Missouri Academy Research in Academia

R e s e a r c h i n A c a d e m i a |0
Research in Academia
Missouri Academy of Science,

Mathematics, and Computing
2017-2018
Introduction
Founded in August 2000, Missouri Academy of Science, Mathematics and
Computing (Missouri Academy or MASMC) is a two-year, residential, early-
college school for high performing and academically talented high school
students. It is located on the campus of Northwest Missouri State University and
is an integral part of the university. The school enrolls domestic and international
students who have completed only 10th grade at their traditional high schools. In
essence, the Missouri Academy replaces the junior and senior years of traditional
high school. The curriculum is rigorous and consists of all college coursework
taught by professors at Northwest Missouri State University.
Missouri Academy students sit in the same classrooms side-by-side with

Dr. Cleo Samudzi, Dean of the traditional university students; and professors have the same high expectations
Missouri Acade my for these students as they do of traditional university students. High school
students who successfully complete this program receive an Associate of
Science (AS) degree, as well as a high school diploma. It is an opportunity for
exceptional students to live and study in a community of peers. The Missouri Academy is highly selective
and only the best and brightest students are admitted to undertake what is arguably one of the most
difficult high school curricula in the Midwest (in the USA).
Most students who attend the Missouri Academy are not only high performing in science, mathematics,
and computing, but are also gifted/ talented in music, arts, the humanities, athletics and community
service. They have performed extremely well at local, statewide and multi-state appearances for Model
United Nations, Boys State and Girls State, community service projects, musical ensembles and theatre.
Student research is a key component in the exploration of a specific topic within a field. Research in
Academia is a student-led project designed to recognize the projects successfully completed by Missouri
Academy students.
Biological Sciences
 Cultivation of bacterial communities from cave sediments
o Seung Hyun Lee, Class of 2015
 Using Characterization Techniques to the Determine the Properties of Porous, Inorganic
Biomaterials
o Seung Hyun Lee, Class of 2015
 Effect of Temperature and Coverage on Cope’s Gray Tree Frog Capture Rates
o Sabrina Olson, Class of 2016
 The Effect of Biological Nitrogen Fixation in Legumes
o Torria Slagle, Class of 2015
 Hereditary Hemochromatosis
o Huixin Du & Heeiae Shim, Class of 2015; Som Singh, Class of 2017
 Immunohistochemical evidence of selective renal sensory denervation after resiniferatoxin
administration in rats
o Som Singh, Class of 2017
Cultivation of bacterial communities from cave sediments

Seung Hyun Lee1, 2, Kathleen Spears 2, Aaron W. Johnson 2, Alisha G. Campbell 2 and James H.
Campbell 2
1
Missouri Academy of Science, Mathematics, and Computing, 800 University Drive, Maryville,
Missouri 64468
2
Department of Natural Sciences, Northwest Missouri State University, 800 University Drive,
Maryville, Missouri 64468
Introduction Site Location. Smallin Civil War Cave, Ozark, MO, USA
(37.1°N, -93.2°W)
Subterranean ecosystems (e.g. caves) are mostly isolated Cultivation. Serial dilution was conducted on a soil sample
from outside sources. This creates biological “islands,” in using 0.85% saline. Cultures were grown on plates
which organisms have evolved separately and differently containing varying pH (5.5- 9.0) and nutrient sources
from those outside of such environments. These (DNA or DNA + arginine) and incubated at 27°C. Colonies
environments are often underexplored, and few of the were chosen based upon representative colonial
microorganisms from such environments have been grown
in a laboratory setting. This research seeks to explore the morphology and re-streaked on the same type of plates on
cultural microbial communities in Smallin Civil War Cave, which they were isolated.
located in southern Missouri within the Ozark highlands.
DNA Analysis. DNA was extracted from the isolates using
Materials and Methods TE/KOH/Tris method, and 16S rRNA genes were
amplified via Polymerase Chain Reactions. Amplicons
were submitted to the University of Tennessee – Knoxville
for Sanger sequencing. Sequences were aligned and
matched with the test strains of identified bacterial species,
using RDP Seqmatch.
Results
Figure 1 –a (upper left). Location of the Smallin Civil

War Cave on the map of Missouri
Figure 2. Number of colony forming units that grew on

Figure 1-b (upper right). Bristly cave crayfish in the each medium (mean of 2 plates of each type). 1’s contain
Smallin Cave DNA and 2’s DNA + arginine as nutrient sources, and all
plates contain vitamins and metals. MES was pH 5.5,
MOPS and HEPES are pH 7.0, and Bicine was pH 9.0.
Figure 1-c (lower left). The Great White Staircase, Smallin
Cave * Lost one plate due to contamination, so did not take a
mean
Figure 1-d (lower right). Waterfall at the entrance of the

Smallin Cave
Table 1. List of closest matches of isolates using NCBI

Blast. Identities show the percentage of identical bases
between our isolate and the sequences in the database.
Strength of matches are measured by e-values (decrease
with stronger matches).
Figure 3. Gel image of amplicons of the 16S rRNA gene of

SL51 – 79. All extracted DNA amplified successfully.
Figure 6-a (top). SL59 on a nutrient agar plate; colony is

Figure 4. Community composition of the isolates from purple with a green center (non-diffusible)
each plate type. Bicine 1 had the most diversity, and
HEPES 1 and 2 had only one isolate cultivated on each. Figure 6-b (bottom). SL59 in Luria-Bertani broth;
produces purple pigment (non-diffusible)
* MOPS4 contains DNA, arginine, and glucose as nutrient
sources and vitamins and metals. Conclusions and Future Directions
• Diverse species of bacteria were isolated from the

cave sediments, most of them Pseudomonas.
Growth was best in HEPES (ph 7.0) and Bicine
(pH 9.0) buffered media.
• Biochemical tests will be run on some isolates for

more accurate identification.
• We will use next generation sequencing of

community DNA to characterize microbial
community structure.
• We hope to further characterize these isolates and

provide a more comprehensive understanding of
the biological community of the cave.
Acknowledgments
• Undergraduate Research Award
• Faculty Senate Grant

Figure 5. Neighbor-joining dendrogram of all isolates and
type strains of their closest NCBI Blast matches. Nodes are
listed with branch support.
Using Characterization Techniques to the Determine the Properties of Porous,

Inorganic Biomaterials
Keisha Avery, Seung Hyun Lee, Anna Rudy, Swarnasri Mandal, Heather K. Hunt Department of
Bioengineering, University of Missouri, Columbia, Missouri
Introduction EDS is used to determine the types of elements found in the

sample. Our goal is to have a pure-silica sample, which
• Biomaterials are synthetic or natural materials would indicate that any carbon present during synthesis
that can be used to construct artificial organs, to was fully removed post-synthesis by solvent extraction,
replace damage bone or tissue, or as an active thermal calcination. The template during synthesis is
coating on implantable devices. organic, which contain carbons. Removing the template
(carbon) to open the pore surface can allow drugs to be
 The biomaterials we are interested in are loaded in the pores.
mesoporous silica (MPS). Their potential
applications include drug delivery systems and
tissue engineering.
 Understanding the physicochemical properties of

these materials will help us further understand
how MPS can be used in these applications.
Here, we examine the structure, porosity, chemical

composition, hydrophobicity/hydrophilicity, and surface
roughness of the synthetic mesoporous silica that could be
used as biomaterials
Background Information
Table 2. shows that a significant amount of the carbon has

been removed from the template when the film that was not
with oxygen plasma was treated with oxygen plasma for 3
hours.
Ellipsometry
Ellipsometry is used to determine the thickness of films and
their refractive index. The refractive index can provide use
with information about the behavior of light when it reacts
with MPS. The behavior could be due to the interaction
between molecules, which could effect the interaction on
light. If the data show there is no interaction between
molecule, then we could possibly add a substance to see if
there is an interaction. Here, we demonstrate typical data
from thin films of cubic mesoporous silica on quartz
substrates.
reflective
Table 3. Summary of index and thickness measurement

Table 1. Summary of characterization techniques
results from ellipsometry.
Results
Energy Dispersive X-Ray Spectroscopy (EDS)

Figure 3. The porous structure of 3D cubic (left) and 2D

hexagonal (right) of mesoporous silica.
Conclusions
Studying the properties of mesoporous silica using
characterization techniques will further our knowledge of
the functions of the material, and will allow researchers to
Figure 1. Best-fit line of the data, MSE: 14.41 (MSE is the determine the appropriate application for these porous thin
mean squared error). The ideal MSE for quart substrates is film materials. This could lead to improvements in
<15. biomedical engineering devices, systems, and therapies.
X-Ray Diffraction (XRD) References

XRD is used to determine the type of structure (2D 1. Sibilia, John P.. A Guide to materials
hexagonal or 3D cubic), order of mesoporous silica thin characterization and chemical analysis. New
films. The order is important to know for different York, N.Y.: VCH Publishers, 1988. Print.
application uses. If it is 3D cubic, then it would be ideal for
a drug releases that is at a slow rate. If it is 2D hexagonal, 2. Glazneva, T.S., Rebrov, E., Schouten, J.C.,
then it would be ideal for a quicker drug release. Paukshtis, E.A. & Ismagilov, Z.R. (2007).
Synthesis and characterization of mesoporous
silica thin films as a catalyst support on a
titanium substrate. Thin Solid Films, 515(16),
6391-6394. in Web of Science Cited 14 times
3. Ratner, B. D. (1988). Surface Characterization of

Biomaterials, Elsewier, Amsterdam.
Acknowledgements
Figure 2. The peaks are more defined after each hour of
template removal. NSF-REU
University of Missouri College of Engineering
Missouri Academy Research Summer
Life Sciences Summer Undergraduate Research Program
Hunt Research Laboratory

Effect of Temperature and Coverage on Cope’s Gray Tree Frog Capture

Rates
Sabrina Olson & J.D. McGhee
Department of Natural Sciences, Northwest Missouri State University, Maryville, Missouri
Abstract Results
• Average Capture Rates
Cope’s Gray Tree Frogs are an important frog species in the state of • Most frogs were captured at pond two, with no frogs
Missouri, and PVC pipe traps can be used to capture these frogs for research. captured at pond three (Figure 1.)
This study examined the effects of foliage cover and temperature on their • Coverage Study
activity as part of a larger analysis observing the effectiveness of PVC pipe • Tubes with more coverage saw more frogs with a higher
traps as a population monitoring tool for this species. A total of 65 PVC pipes variation (Figure 2.)
were placed at various locations in and around four ponds at MOERA. Tube • Temperature Study
temperature was recorded in tubes where a frog was captured, as well as a • No relationship between capture rates and tube
random tube in the area, using a simple mercury thermometer. Canopy temperature (Figure 3.)
coverage was measured above PVC pipe traps each week, and pipe use by
tree frogs was analyzed graphically. While no significant relationship was
found between frog use of pipes and pipe temperature, there did appear to be
a relationship between canopy cover and pipe usage. However, this
relationship was non-normal and highly varied. Data suggests that canopy
coverage may be of greater importance in habitat selection criteria than perch
temperature and warrants greater study.
Introduction
Copes Gray Tree frogs (Hyla chrysoscelis) are a common species of tree frog
found throughout Missouri. Ranging from 1.25 to 2 inches (3.2-5.1 cm) in
length (Slone), Gray Tree Frogs can be found in a variety of colors ranging
from gray to light green depending on activity and environment.
As tree frogs are amphibious, they are unable to internally regulate their body
temperature, relying instead on external sources to maintain a stable
temperature. PVC pipe traps offer frogs a refuge - one in which they can
maintain a balanced body temperature. This study examined the effect of
shade coverage and tube temperature in relation to frog capture rates.
Hypothesis
Tubes with a lower temperature as well as tubes with more coverage will
attract a larger percentage of Cope’s Gray Tree Frogs.
Methods
• 65 PVC pipes placed at four different ponds in the MOERA area

• Each pipe was one meter long if placed on the ground or
60 cm long if placed on a tree
• Pipes were arranged randomly so that:
• One pipe placed two meters from the tree
facing away from the pond
• One placed two meters from the tree facing
towards the pond
• One placed on the tree
• One placed five meters from the tree facing
towards the pond
• Data was collected every Thursday and Friday over a three month
period
• Analyzed using a students t-test to compare capture. vs
random tubes
Discussion
This study showed that traps with more coverage saw higher capture rates,
but there was a large amount of variation in data. It was noticed that once a
particular frog was found in a certain tube, that specimen continued to be
recaptured in that particular trap on a regular basis. Further research is needed
to determine if such behavior in the frogs is influenced by foliage coverage or
if it is a function of these amphibians simply return to a location that offers
protection from predators (such as inside the PVC-pipe taps used in this
study).
References and Acknowledgments

Jonathan Slone. 2016. “Cope’s Gray Treefrog (Hyla chrysoscelis).” Savannah
River Ecology Laboratory. <http://srelherp.uga.edu/anurans/hylchr.htm>.
Thanks to my team mates, Brett, Alex and Abby and to my professor Dr.
McGhee
The Effect of Biological Nitrogen Fixation in Legumes

J Torria Slagle, Hossain Md Shakhawat, Gary Stacey
Missouri Academy, Northwest Missouri State University; Division of Plant Sciences, University of Missouri, Columbia;
Department of Biochemistry, University of Missouri, Columbia; National Center for Soybean Biotechnology; 5C. S. Bond Life Center
Background 5.
Plants use nitrogen to build proteins and it is a crucial

element for the growth and development of plants. Yet
even though nitrogen makes up 78 percent of our
atmosphere many plants cannot convert the N2 into the
NH3 form that is needed for the nutrients. Many plants
receive the nitrogen artificially through fertilizer and other
methods. These methods require energy such as fossil fuels
to make and after use can cause pollutants in the form of
runoff material. Legume plants such as soybeans (Glycine
max), Lotus japonicas , and Medicago trancatula do not
require artificial nitrogen because certain bacteria (specific
to each type of plant) is able to enter into the host roots and
form symbiotic organ (physically seen as nodules) and have
a mutual relationship with the plants. The plants provide
the bacteria with the energy as a carbon source. While in
return the bacteria convert the atmospheric N2 to NH3 for
the plant. Compare plants to see the effects of biological nitrogen
fixation.
An analysis of M. trancatula mutant having a Tnt1 insertion
shows a strong phenotype in nodule formation as well as Figure 1: Nitrogen fixing bacteria enhance plant growth
growth defects such as shorter roots and shoots. In rare and development.
cases the mutant can form very few, small nodules. Thus, (A) Glycine max and (C) Lotus japonicus results: Nitrogen
the mutant could not fix biological nitrogen fixation. In is a component of chlorophyll, which is important in
contrast, the wild type plants are able to infect the roots and converting the sunlight to sugar otherwise known as
convert the N2 to NH3 and use it as nutrients, grow photosynthesis. Chlorophyll is also the substance that
significantly larger, healthier, and have thicker roots with makes the shoot and leaves green. The rate of
more nodules than the mutant plants. photosynthesis increases when there is an abundant supply
For sustainable agriculture, food production, and minimize of nitrogen. As our data supports plant growth will improve
environmental harms, biological nitrogen fixation can aid with sufficient quantities of nitrogen and the leaves will
in growing healthier plants without the need for artificial turn green. The bacteria inoculated in the plants are able to
fertilizer. This presentation will show the results of legume use the nitrogen from the atmosphere to aid plants in
plants that are inoculated with or without bacteria. It will photosynthesis. Without nitrogen the plant cannot carry out
also include the phenotype results between mutant and wild photosynthesis as well and the lack of energy conversion
type Medicago trancatula shows smaller plants (shoot and root lengths decrease).
Without the bacteria to convert nitrogen, the plant’s
chlorophyll is lacking one of its essential elements and
Method therefore the plants appear yellow.
(B) Medicago trancatula inoculated with/without the
1. Germinate the seeds; each plant seed has a different bacteria. The inoculated root and shoot lengths are longer
procedure. than the uninoculated. The inoculated leaves show green,
while the uninoculated leaves appear pink, because
2. Inoculate the plants with host specific bacteria, such as:
Medicago trancatula: Sinorhizobium meliloti
Lotus japonicus: Mesorhizobium loti
Glycine max: Bradyrhizobium USDA110
3. Measure the length of the plant’s roots and shoots.
4. Stain the roots to observe the bacterial infection

phenotype in the nodules.
uninoculated plants accumulated anthocyanin due to lack of

nitrogen sources.
Figure 2: Nodule formation and Nitrogen fixation in

legumes.
Inoculated plants, Lotus japonicus (A) and Medicago
contrast, without bacteria plant roots remain non-nodulated

and no nitrogen is fixed.
Figure 3: Phenotype of Medicago trancatula seedlings before
they were planted in the soil.
Figure 4: Root-Nodule phenotype of M. trancatula after 2

trancatula (B) form nodules by the presence of bacteria. In weeks of S. meliloti inoculation. Upper panel shows wild
type and bottom panel shows one of the insertion mutant of

corresponding wild type.
Figure 5: Nodule phenotype of M. trancatula after 2

weeks of inoculation. The blue stain indicated the bacteria
contained the Lacz Gus reporter gene.
Figure 6: Growth phenotype of shoot and root, and

quantification of nodule numbers after S. meliloti
inoculation in M. trancatula wild type and an insertion
mutant.
Results: Longer shoot and root length, and increased

nodule numbers were seen when wild type Medicago
trancatula plants were inoculated with the S. meliloti.
However, the length of shoot and root and nodule numbers
decreased significantly in the insertion mutant as compare
to the wild type plant. Note, in the mutant plants bacteria
are unable to penetrate to colonized the roots for nodule Future objectives:
formation.
Understand the complex mechanism of nodulation in
legume plants and employ this system to non-legume
Conclusion crops, such as, maize, wheat, rice to establish symbiotic
relationship. Ultimately, this will remove or reduce the cost
Nitrogen fixing bacteria has the ability to fix atmospheric of chemical fertilizer and its use in the agriculture field in
nitrogen. turn saving our environment from pollutants, i.e. the
Only legume plants form symbiotic relationship by the runoff of chemical fertilizers.
formation of nodule with their host specific bacteria and fix
biological nitrogen. Thus, legume plants does not require Understand the complex mechanism of nodulation in
artificial nitrogen fertilizer for their growth and legume plants and employ this system to non-legume
development. crops, such as, maize, wheat, rice to establish symbiotic
The insertion mutant of Medicago trancatula unable to relationship. Ultimately, this will remove or reduce the cost
form successful symbiotic relationship with their bacterial of chemical fertilizer and its use in the agriculture field in
partner, as a result, the mutant plants showing severe turn saving our environment from pollutants, i.e. the
growth defects. runoff of chemical fertilizers.
Hereditary Hemochromatosis
Huixin Du, Heeiae Shim, Som Prabh Singh, M.Rafiq IsIam
Laboratory of Biochemistry, Northwest Missouri State University, Maryville, MO 64468
Abstract Other mutations that cause this disease have also

been identified, including one known as H63D.
Hereditary hemochromatosis (HH) is a
common autosomal recessive disorder of The disease is treated by removing blood (known as
iron overload among Caucasians of phlebotomy) from the patient in order to lower the
northern European descent. Over 85% of all overall level of iron in the blood.observed in the
cases with HH are due to mutations in the ionization spectra as the integer multiples of the
hemochromatosis protein (HFE) involved in photoelectron half wavelength fit the molecular
iron metabolism. Although the importance in redii at certain energies [10]. The effect also
iron homeostasis is well established, the accompanies a beating modulation in the ionization
mechanism of sensing and regulating iron spectra as a signature of C60 molecular width [11].
absorption by HFE, especially in the
absence of iron response element in its gene, Methods
is not fully understood. Recently we have
Human HFE promoter fragment In the promoterless
shown that PARP1 binding to an inverted
luciferase reporter vector pGL3-Basic (Promega)
repeat located at -931/-918 of the HFE
was PCR generated using primer pairs, digested and
promoter may serve as a novel iron sensing
cloned at sites of the vector.
mechanism as PARP1 cleavage via iron
treatment relieves HFE transcriptional All PCRs were performed in similar fashion:
repression (BBA 1829:1257-65, 2013). In following a denaturation step at 95°C for 3 min, 30
this study, we present the ubiquitous cycles of 94°C for 30 sec, respective annealed
transcription factor, Sp1 plays a role in temperature (53-60°C) for 45 sec, and 72°C for 45
HFE expression and rescues PARP1 sec, with a final extension of 7 min at 72°C.
inhibition. It is known that Sp1 also
upregulates PARP1 (via binding to a site on
the promoter) as well as physically interacts
with PARP1. We believe that Sp1
upregulates HFE transcription in two ways:
via binding to a Sp1-site on the HFE
promoter, and by reducing PARP1 pool
available for binding to the HFE promoter
through Sp1-PARP1 interaction.
Conclusions
HFE Gene
Sp1 upregulate HFE expression
HFE is a gene that is located on chromosome 6
Sp1 binds to a site on the promoter PARP1 to
Cases of HH result from a common mutation in this promote expression
gene, known as C282Y.
R e s e a r c h i n A c a d e m i a | 10
References
Pelham, C., Jimenez, T., Rodova, M., Rudolph, A.,
Chipps, E., & Islam, M. R. (2013). Regulation of HFE
expression by Poly(ADP-ribose) polymerase-1
(PARP1) through an inverted repeat DNA sequence
in the distal promoter.Biochimica et Biophysica
Acta, 1829(12), 1257–1265.
Fact Sheet : Hemochromatosis. (n.d.). Retrieved

March 19, 2016
Putting DNA to Work - Inherited Disease -

Hemochromatosis. (n.d.). Retrieved March 19, 2016,
Immunohistochemical evidence of selective renal sensory denervation after

resiniferatoxin administration in rats
Som P. Singh, Arthur D. Loewy, Ph.D, , Mark M. Knuepfer, Ph.D1Missouri Academy, Northwest Missouri State University;
Department of Pharmacology and Physiology, Saint Louis University, St. Louis, MO
63104
Department of Anatomy and Neurobiology, Washington University School of Medicine, St.
Louis, 63110
Abstract reveal the neurotransmitter content of nerves. Neuropeptides

substance P (SP) and calcitonin gene-related peptide (CGRP) serve
as afferent nerve markers. Renal afferent nerves are located
Essential hypertension affects millions of people worldwide and is predominantly in the renal pelvic wall. In contrast, neuropeptide Y
a central factor to complications such as heart failure, stroke, (NPY), norepinephrine (NE), and tyrosine hydroxylase (TH) were
dementia, and chronic kidney disease. Resistant hypertension, a used as efferent nerve markers. These are found predominantly on
condition which cannot be treated by present drug therapy, is the blood vessels and in the renal cortex (4, 8).
estimated to affect 10-50% of hypertensive patients in the US. It is not known why renal denervation lowers arterial blood
Renal denervation is a surgical technique used to treat the causes pressure in resistant hypertension. Furthermore, since renal nerves
of resistant hypertension. However, the mechanisms for the are mixed with afferent and efferent sympathetic nerves, renal
antihypertensive effects of renal denervation are not known. We denervation after radiofrequency ablation is nonspecific (4, 8).
hypothesized that renal denervation reduces arterial blood pressure Therefore, it is not known if the antihypertensive effects renal
due to the loss of afferent (sensory) nerves. Therefore we proposed denervation is due to removing afferent, efferent, or both. We
a novel treatment to selectively remove afferent nerves using the sought to determine if selective afferent renal denervation is
TRPV1 agonist, Resiniferatoxin (RTX). In this study, to verify the possible using resiniferatoxin.
effectiveness of selective loss of renal afferent nerves, we used We hypothesize that selective denervation of renal afferent nerves
immunohistochemical procedures to examine the rat kidney. We is possible by administering resiniferatoxin (RTX) to the renal
determined neuropeptide concentrations in the renal pelvis two pelvic region. RTX is a selective agent that sensitizes transient
weeks after treatment. There was a 63% decrease in afferent receptor potential vanilloid 1 (TRPV1) receptor-expressing sensory
neuropeptide CGRP activity after RTX treatment. The results nerve endings. TRPV1 receptors exist exclusively on afferent
suggest that the RTX treatment can be used to effectively reduce nerves. RTX depletion of CGRP immunoreactivity will verify
renal afferent nerves selectively. Using this procedure, we hope to selective renal afferent denervation (10, 11).
test whether renal afferents contribute to the development and/or
maintenance of hypertension.
Materials/Methods
Animals and General Procedures
Introduction Healthy male Sprague-Dawley rats weighing between 220 to 300
grams from Envigo (Indianapolis, Indiana) were used for this
It has been estimated that hypertension (high blood pressure) experiment. All procedures were approved by Saint Louis
affects over 970 million people worldwide, including 1 in every 3 University’s Institutional Animal Use and Care Committee and
American adults(1).Essential hypertension, of unknown etiology, complied with the National Institute of Health guidelines set forth
contributes to the development of heart and renal failure, coronary from the Guide for the Use and Care of Laboratory Animals.
artery disease, dementia, and stroke. Hypertension is defined as a Rats were anesthetized using 2.5 percent isoflurane and intubated
systolic blood pressure over 140 mmHg and/or a diastolic blood with 100% oxygen. Rats were shaved and scrubbed with Betadine
pressure over 90 mmHg (2). Due to lifestyle changes coupled with surgical scrub and allowed to sit for five minutes before washing
an aging population, the worldwide incidence of hypertension is briefly with 70 percent ethanol. The rats were then placed on a
expected to be 1.6 billion within the next ten years (1, 9). Many sterile drape over a heating pad on low until surgery. All surgical
antihypertensive treatments have been developed such as alpha- procedures were done using aseptic technique (2011). After
and beta- adrenoreceptor antagonists, diuretics, vasodilators, surgery, rats were monitored hourly and were given 20 mg/kg
calcium channel blockers, angiotensin-converting-enzyme (ACE) Carprofen for pain relief and antibiotics (enrofloxacin, 10 mg/kg) .
inhibitors, and aldosterone antagonists (2). Despite these therapies,
these treatments only alleviate the symptoms, and not the cause of Resiniferatoxin Administration
hypertension. Moreover, it is estimated that 10-50% of all A laparotomy was performed on the anesthetized rats to expose the
hypertensive patients in the US have resistant hypertension (3). In left renal ureter. This ureter was later cannulated retrogradely with
these patients, despite antihypertensive drug treatment, arterial a gas-sterilized, dual lumen cannula. The right kidney was the
pressure is still elevated. Recently, renal denervation has been control. Next, the renal pelvis of the left ureter was exposed to 1.6
proposed for treatment of resistant hypertension (3). Catheter- µM resiniferatoxin for ten minutes with a slow infusion of 150 µL
based renal denervation using radiofrequency ablation has been allowing outflow through the second cannula. After resiniferatoxin
shown to be effective in reducing arterial pressure (4). was properly administered, intraperitoneal saline was given to
ensure proper hydration to the rat. Resiniferatoxin was not
The renal nerves consists of efferent sympathetic nerves that administered to the control. After the operation, the cannula was
project from the central nervous system to the kidney, and afferent removed and the ureter repaired with 11-0 ethicon suture (Ethicon
sensory nerves, which project from the kidney to the central J311H). All other wounds were repaired with a 4-0 monofilament,
nervous system in response to mechanoreceptor and/or nonabsorbable suture (Ethicon 699G) and treated with Bactroban
chemoreceptor activation (4, 5). Afferent and efferent renal nerves cream. Rats were monitored daily for 2-4 weeks to allow time for
can be differentiated using immunohistochemical markers that nerve and nerve terminal degeneration(15).
Immunohistochemistry developed a procedure to selectively produce renal afferent sensory

The rats were deeply anesthetized with 4-5% isoflurane and denervation following intravascular resiniferatoxin administration
administered 0.5 mL injectable lidocaine (2%) and 0.5 mL heparin, into the rat renal pelvis. We hypothesized that resiniferatoxin
then perfused transcardially with phosphate buffer solution, would deactivate TRPV1 receptors in the renal pelvis which would
followed by 4% paraformaldehyde. The perfusion was done using subsequently deplete CGRP-immunoreactivity. The principal
a 14 gauge needle inserted in the apex of the left ventricle and finding of this experiment was that 2 weeks following
advanced into the ascending aorta. The right atrium was cut to resiniferatoxin treatment, there was a lowered CGRP
allow fluids to drain. As soon as the needle is inserted, a flush of immunoreactivity than compared to control. Furthermore, the
warm phosphate buffer solution was infused for a total of 60 mL. change in TH concentration after RTX treatment was insignificant
This was followed by 60 mL warm paraformaldehyde (4%), and to show reduction of efferent sympathetic activity. The reduction
then by approximately 500 mL of ice cold paraformaldehyde at the in the afferent sensory nerve marker’s activity supports our
rate of 100mL/min for five minutes. Next, the kidneys were hypothesis.
rapidly removed, cut in the transverse plane with a scalpel, and We believed CGRP-immunoreactivity would deplete after RTX
placed in 30% sucrose fixative at 4⁰C. to be processed for treatment due to results similarly found in previous experiments
immunohistochemistry (n=6) (8). which showed that renal sensory denervation is possible with
Single label immunohistochemistry was performed using the DAB capsaicin (Peterson et al. 1989). Resiniferatoxin and capsaicin are
technique on each renal section. The polar ends of a transverse both naturally occurring ingredients found in hot peppers. Both act
plane of the kidney was cut to isolate the renal pelvis. A cryomold on transient receptor potential vanilloid 1 (TRPV1) receptors.
was filled with an embedding media, Octamer Transcription Factor These are the receptors that respond to heat in mammals and are
(OCT). The renal pelvis was placed prone into the OCT media and known to create selective loss of sensory nerves. Jancso-Gabor
allowed to sit for 30 minutes. The sample was then frozen in an ice (1980) had shown that the afferent nerve marker CGRP has
bucket at -80⁰C and cut into sections using a cryostat and placed TRPV1 receptors localized on these receptors. It is known that
on a slide. resiniferatoxin is a thousand times more potent than capsaicin.
The renal pelvic sections were stained with the primary In our previous studies with capsaicin, we quantified afferent and
antibodies:calcitonin gene related peptide (CGRP), tyrosine efferent nerve marker concentration through ELISA to show that
hydroxylase (TH), protein gene product 9.5 (PGP 9.5) and stored functionally capsaicin selectively denervates afferent nerves. Each
overnight in a humidity chamber at 4⁰C. Thereafter, the slides of these previous studies suggests that resiniferatoxin also
were introduced to the secondary antibodies: donkey anti mouse functionally depletes afferent nerves. However, in this study we
Cy 3 and donkey anti rabbit AF 488 stored placed back into the aimed to verify neurochemically that RTX selectively denervate
humidity chamber at 4⁰C for 1 hour. the renal afferent nerves through immunohistochemistry.
Data Analysis We sought to to quantify nerve marker concentrations similar to
Slides were analyzed using darkfield microscopy with an ELISA in order to see how much denervation occurs. However,
OLYMPUS VS120 virtual slide microscope. The CGRP and TH due to afferent nerves being predominantly in the renal pelvis, the
concentrations on the images were quantified through ImageJ. ELISA technique does not show the localization of where the
Sources of Drugs denervation occurs, and includes concentration of other parts of the
All drugs used in this experiment were obtained from the Sigma- kidney which were not administered RTX. Therefore, we looked
Aldrich corporation with the exception of Baytril and Rimadyl upon immunohistochemistry to localize the afferent and efferent
(Comparative Medicine). Injectable lidocaine was obtained from nerves in the kidney, while quantifying concentrations of RTX
Sparhawk Laboratories (Lenexa, Kansas). Heparin was obtained treatment. As seen in the result by Mulder et al. (2013),
from Abraxis Bioscience (Schaumburg, Illinois). immunohistochemistry of the renal pelvis allowed us to easily
visualize total denervation through cutting nerves and
administering 10 percent phenol. We aimed to produce similar
Results result, but with the novel RTX-treatment. The 63 percent CGRP
Right rat kidneys were the control group. The average CGRP decrease seen in Figure 1 indicated that resiniferatoxin
concentration per area of the control kidney was 3.9366836 . In
10-5
deafferentated the renal pelvis.
contrast, the average CGRP concentration per area of the left
(treated) kidneys which underwent resiniferatoxin administration Our study concludes through immunohistochemistry that renal
into the pelvic area was 2.4919877 . Figure 1 shows that the RTX
10-5
denervation of afferent nerves is the mechanism that results in the
treated kidneys had a 63 percent decrease in CGRP antihypertensive effects of renal denervation. With the failure of
immunoreactivity compared to the control. drug treatment through ganglionic blockers, ACE inhibitors, and
The average TH concentration per area was also determined more to only alleviate symptoms, renal denervation was the first
immunohistochemically. The average TH area of the control was procedure that treated the cause of hypertension. Furthermore, with
7.81161 ,while the average TH concentration per area of the RTX
10-5
resiniferatoxin being more potent than capsaicin and being
treated kidneys was7.450115 . There was a less than 5 percent
10-5
administered at the prime location of the disease, this novel
decrease in CGRP immunoreactivity in RTX treated kidneys than procedure treatment could be a safer antihypertensive treatment in
the control. humans.
Figure 2 shows the immunohistochemistry of the left RTX treated
transverse cut pelvic wall and the right control transverse cut
kidney pelvic wall after 2 weeks. The membranous pink structure
is the renal pelvic wall stained for the antibody PGP 9.5 which is
specific for neurons. CGRP and TH is labeled in green as the
specific afferent nerve marker. DAPI antibody counterstain all
non-CGRP or TH cell nuclei. The renal pelvis is the dark area
located inferior to the wall where CGRP concentration per area
was calculated.
Discussion
In this study, we investigated whether resiniferatoxin would
decrease CGRP immunoreactivity in the renal pelvis. We
Left Kidneys-RTX treated Right Kidney-Control
Figure 2: Immunohistochemistry of the renal pelvis of RTX-treated left kidneys and the contralateral control kidneys of the rats.
CGRP (green) concentration on the renal pelvic wall(pink) is significantly lower in all
RTX-treated kidneys. Photos taken through OLYMPUS VS 120 Slide Scanning Microscope
Immunohistochemistry Key
PGP 9.5 Stain- Pink
CGRP- Green
DAPI (non-CGRP) stain- Blue
Acknowledgments
We thank Nicole B. Hoffman-Schepers for assistance with animal care procedures, and Robin Weinberg, Ph.D, St. Louis
Community College at Forest Park for comments that greatly improved the manuscript. We would also like to show our gratitude
to the STARS Program for the opportunity to sponsor for this project. We are also immensely grateful to Cleo Samudzi, Ph.D,
Missouri Academy of Science, Mathematics, and Computing, for initial guidance.
Chemistry
 Stability Analysis of Metal Oxide Compounds Used in Combustion Reactions by Computational
and Physical Method
o Jaewoo Kim, Class of 2017
 Effective Diameters of Coated Naproxen Influenced by Concentration of Methocel E6 and Kollidon
VA64
o Xinyue Chen, Yiming Ma, Shuyan Li, Class of 2016
 Additive Manufacturing of AZ31 Magnesium Alloy
o David Wang, Class of 2017
 Preparation and Characterization of Naproxen Nanosuspensions
o Nabig Chaudhry, Class of 2013; Sarah Minkler & Lyndsey Kirkorian, Class of 2014;
Heemoon Jeong2 &Jae Hyun Park2, Class of 2015
Stability Analysis of Metal Oxide Compounds Used in Combustion Reaction

by Computational and Physical Method
Jaewoo Kim Byul Sohn Jaewon Lim
Choice Research Group
Prior research results have been controversial regarding the
Abstract efficiencies of each catalyst. One paper concludes that the
efficiency of platinum soars above the other catalysts. On
The theoretical structure of feasible catalytic compound is the other hand, Pt is also seen as ineffective while Ni and
presented in this study. The physical activity and chemical Ag prove to be especially reactive.
stability of catalytic compounds are proposed after
modeling and analyzing the molecule based on the
compounds’ electron structures, and bond lengths and bond
Materials & Methods
strengths. The ultimate goal of presented research is to
achieve better selectivity in producing green energy. Also This project aims to determine the catalyzing ability of
convergence test of the proposed molecules is carried out to Titanium compounds using a computational chemistry
determine the stability of the metal oxides. Numerical and method, also using programs such as Gamess and
computational methods are used in order to model the Chemcraft, in an effort to discover the optimal method
electron properties of the compounds. Computational steps and to compute the measures of catalytic ability. Density
(N) versus energy (kcal/mol) curves for each metal Functional Theory (DFT), a computational chemistry, is
compounds are presented to check the stability and used in order to model the electron properties of the
convergence of the molecules. compound.
Introduction Gamess is a program that allows performing such

computations for a compound. It takes an input file of a
Many studies have demonstrated large enhancements of defined format and converts it into an output describing
catalytic behavior due to the role of the oxide-metal the molecule and the reaction. Chemcraft is another
interface, wherein charge plays a crucial role in catalytic program that takes the output from Gamess and
chemistry. Catalytic oxidation reactions are crucial for expresses it as a model. This program shows the
chemical synthesis in pharmaceutical and petrochemical optimized geometry energy levels and fully determines
industries. Every place for oil production is becoming more the theoretical values of the structure’s atomic properties.
and more expensive. Metals such as Pt, Pd, Rh, Ru, Cu, and Also, Avogadro is an open-source molecular editing
Ni have been widely used as prominent catalysts for
program with an auto-optimization feature that
industrial applications, which include production of a high-
determines the theoretical 3 values of the structure’s
octane gasoline, and chemical productions as well as
cracking, refining, and reforming of petroleum. At the end atomic properties. It allows users to build virtually any
of the study, the catalytic efficiencies of various Ti molecule with the optimized geometry according to
compounds will be modeled and explained based on the various force field options. While UFF (Universal Force
compound’s 2 electron structure and how the catalytic Field) is suitable for optimizing most molecules, we first
efficiency could be improved even more by forcing the optimized our molecules with GAFF (General Amber Force
catalyst to react with methane in different ways. Field) and then with UFF. This approach often produced
lower molecular energy and more regular geometry than
Methanol is formed through the partial oxidation of optimization with UFF alone.
methane. Methane can be a source of energy by itself, and
it is a cleaner way to produce nearly the same efficiency In recent studies, several catalytic processes for the direct
because methane will release CO2 and other dangerous hydroxylation of many aromatic compounds have been
byproducts. reported using a metal catalyst. Although the process is
valid, the actual mechanism behind the reaction is still
The properties of an atom such as its momentum, position, unclear. This project attempts to find the reaction
and energy level are defined by the electron structure. The pathway and define the compounds used in the
catalytic efficiency of a compound depends on its electron
conversion.
structure. Electrons with the right amount of energy and at
the right location would increase the efficiency. To react in These steps of equations show how theoretically the
different ways, we can change the position of the atoms of methanol economy works.
the molecules we are studying and see how that would
affect results. Catalytic oxidation reactions is another way
of describing the types of reactions similar to methane to
methanol, and the oxidation reaction facilitated by a
catalyst.
2. Titanium dioxide trichloride (Ti2O2Cl3) – GAFF

First step (1) is the use of Titanium chloride to react with Method
an oxide. The symbol Y is a generic leaving group. Most Also, when the GAFF method was employed, this molecule
cations do this way and this step shows how TiClO is is considered to be a possibly stable ionic compound due to
created. its delocalization of electrons.
Next step (2) is the actual conversion of methane to
methanol. Notice the TiCl is recycled so it can be used for
the first equation again. On the third step (3), the leaving
group can bind with oxygen again to make for the other
reactant for the equation on the first line. This is how the
recycling of materials exemplifies the methanol economy.
Results
1. Titanium dioxide trichloride (TiO2Cl3)
In Figure 1, the Ti and the Oxygen ion are bonded in a
linear configuration. Possible this molecule is considered to
be a stable ionic compound but data show that both are
unstable. Optimization convergence shows that Titanium
dioxide trichloride (TiO2Cl3) is better than the TiO3Cl2
molecule catalysts.
3. Titanium dioxide trichloride (Ti2O2Cl3) – UFF

method
From the bond structures shown in Figure 3, the Ti-O bond
is relatively weak compared to the O-Cl bond. The weak
Ti-O bond strength indicates a propensity toward an ionic
bond or just a weaker and partial bond, meaning flexibility
in reaction. The following figure shows Ti2O2Cl4 with
central atom O when the GAFF method was employed.
Discussions and Conclusions

In the light of the promising use of Ti complexes, we wanted to
study their thermodynamic stability. For this purpose, we used the
computational programs to model, optimize, and compare the
It can be seen that the oxygen atom is spontaneously resulting molecular energy of the clusters. The main objective of
forming bonds with the rest of the molecule. The Table 2 the project was to investigate proposals from experimental papers
illustrates how the bonds in the molecule form. hypothesizing that Ti based catalysts are effective for converting
methane to methanol and to reject or accept the hypothesis stated
in
some experimental papers suggesting that Ti in high oxidation
states (3+ and 4+) might be an efficient catalyst.
Transition metal can be used for the conversion of methane to
methanol, as past research has shown that nickel and palladium
work reasonably well to produce methanol in the presence of
ozone. In this paper Ti compounds are modeled using computer
and explained based on the compound’s electron structure.
The theoretical structure of each feasible catalytic Ti compounds
has been studied in this project. Based on the predicted stability of
each molecule, it can be predicted which compound can be used
most efficiently to catalyze the reaction for the methanol economy.
The results in the quantum chemical calculations in this paper have
4. Titanium dioxide tetrachloride (Ti2O2Cl4) shown that Ti2O2Cl4 is very unstable, and therefore it cannot be
This configuration is considered to be unstable due to its used as a catalyst. It is not stable as a compound, thus rejecting the
hypothesis. It can be seen that the oxygen atom is spontaneously
angle strain. The Ti and the two Cl ions are bonded in a
refusing the rest of the molecule. Although these computations
non-planar configuration. Optimization convergence of the have established that Ti2O2Cl3 is the most efficient compound,
Ti2O2Cl4 is very slow compared to the molecules above in engineers still have to design a commercially feasible way to
1, 2, and 3. chemically produce Ti2O2Cl3.
Also other metal chloroxide, such as Ti3Cl2O3 and Ti4Cl3O2, or

more compounds need to be computationally studied further. Since
Ti has many oxidation numbers, the structural
optimization of other titanium oxychlorides (TixOyClz; x = 2−4, y
= 1, 3−6, and z = 2, 4, 6) and thermos-dynamical stabilities of the
compounds need to be assessed.
Effective Diameters of Coated Naproxen Influenced by Concentration of

Methocel E6 and Kollidon VA64
Xinyue Chen, Yiming Ma, Shuyan Li, and Shelley Riley
Department of Natural Sciences, Northwest Missouri State University, Maryville, Missouri
Abstract aliquot of each nanosuspension was diluted with nanopure
water and filtered (Nylon Acrodisc Syringe Filter (0.1 mm
Previously, it has been found that 0.6%(w/v) of pore size), and then transferred to a cuvette for analysis.
Kollidon VA64 (Vinylpyrrolidone-vinyl acetate
copolymer) and Methylcellulose E6 stabilizers have
effectively coated Naproxen to allow the manufacture and
long term stability of drug nanoparticles. In the current
experiment, lower concentrations of the two stabilizers
were explored and the effectiveness of both materials was
compared at concentrations of 0.1% and 0.3% (w/v). Both
stabilizers were effective at levels of 0.3% (w/v). Kollidon
VA64 at 0.1% (w/v) was ineffective in producing and
maintaining particle size. Methocel E6 at 0.1% (w/v) was
initially effective in producing nanoparticles, however
agglomeration and particle growth occurred within one
week of manufacture.
Introduction
Nowadays drug makers are able to formulate medicines
as encapsulated nanoparticles which can be effectively
dissolved in an aqueous medium and transported across the
intestinal mucosa of human body to cure the illness. Studies
show that although these drug particles are small enough to
do the job, the drug may still be ineffective due to the
agglomeration of the nanoparticles. There are two ways to
stabilize the particles and prevent agglomeration: 1) use
surfactants as a coating and 2) use a polymer as coating of
the nanoparticles. Naproxen, is a nonsteroidal anti-
inflammatory drug used in the treatment of arthritis and
musculoskeletal inflammation and moderate pain and was
used as study the effect of low concentrations on the
particle size of drug. the model drug. In the current
research 0.1% and 0.3% (w/v) concentrations of Kollidon
VA 64 (surfactant) and Methocel E6 (polymer) coating
materials were used and Dynamic Light Scattering was
used to determine the particle size distributions to
Methods
Naproxen nanosuspensions (5% w/v) were prepared by
combining the sodium salt of naproxen and 0.1% or 0.3%
(w/v) stabilizer solution. Yittria-Stabilized Zirconium Discussion
Beads (0.8 mm) were added and suspensions were milled
on jar mill at 100 rpm for 5 days. Nanosuspensions were The tables of results shows that:
stored in polypropylene conical tubes Particle size analyses
were performed using Dynamic Light Scattering. A 20 mL
• Methocel E6 0.1%(W/V) is more effective than However, the timeline used in this research is too short for
Kollidon VA64 at 0.1%(W/V) in short-term evaluating the long-term stability of drug coating.
period(after the first week and the second week). Therefore a further study on longer time period is needed.
• Kollidon VA64 0.1%(W/V) is more effective than
Methocel E6 at 0.1%(W/V) in long-term period(after References
the first month).
• Methocel E6 and Kollidon VA64 at 0.3%(W/V) both Merisko-Liversidge, Elaine M., Liversidge, Gary G.. 2008.
are effective stabilizers for Naproxen suspension. Drug nanoparticles: formulating poorly water-soluble
• Drug practices that stabilized with surfactant Kollidon compounds(USA). Toxicologic Pathology 36:43-48.
VA64 at 0.3%(W/V) can prevent them to agglomerate
efficiently. Merisko-Liversidge, Elaine M., Liversidge, Gary G. and
Cooper, Eugene R. 2003. Nanosizing: a formulation
This research gives a further reference for drug particles
approach for poorly-water-soluble compounds. European
coating materials and concentration:
Journal of Pharmaceutical Sciences 18: 113-120.
We can use surfactant Kollidon VA64 at 0.3%(W/V) in
Field, Simon. Naproxen. http://sci-
drug manufacturing process so than the drug practices can
toys.com/ingredients/naproxen.html
still keep small enough to do the job after being stored in a
period of time.
We cannot make sure that is Kollidon VA64 at 0.3%(W/V)

effective to other drug particles as well as to Naproxen.
Additive Manufacturing of AZ31 Magnesium Alloy

David Wang, Elizabeth Goetz, Qilin Guo, Lianyi Chen
Mechanical and Aerospace Engineering, Missouri University of Science and Technology
Background
• Additive manufacturing is a new growing

technology with many potential uses and
materials.
• AZ31 is a magnesium alloy that is both stronger
and lighter metal but harder to print.
• The research that has been done on how to 3D
print magnesium and its alloys uses layers of
powder causing the product to be less dense
and weaker Potential parameters found:160W
at 60 mm/s for a pulse laser and 105-150W at 35-
50 mm/s for a continuous wave laser
considering 0.3 melting depth but this was
found assuming a linear correlation and is
inaccurate
• Melting Point of AZ31 is 922 K
Preparation and Characterization of Naproxen Nanosuspensions

Shelley Rabel Riley, Nabig Chaudhry, Heemoon Jeong, Jae Hyun Park, Sarah Minkler, Lyndsey
Kirkorian
Department of Natural Sciences, Northwest Missouri State University
Missouri Academy of Science, Mathematics, and Computing
evaluated using reversed-phase HPLC. Samples and

Introduction standards were diluted in Methanol:H2O (2:1, v/v) and
injected (10 mL). A gradient method from 10% to 90%
The utilization of high-throughput screening methods in the Mobile Phase B over 25 minutes was used with detection at
discovery of pharmaceutical compounds has resulted in the 331 nm. Mobile Phase A: H2O with 0.05% (v/v)
identification of drug candidates of very high potency and
Trifluoroacetic Acid Mobile Phase B: Acetonitrile with
selectivity at the expense of other physical and chemical
properties of the compound, most notably aqueous 0.05% (v/v) Trifluoroacetic Acid
solubility, which are required for development of a product
with acceptable performance. One approach that has been
Results
used to address the delivery of poorly soluble drugs is the
use of drug nanosuspensions. The thermodynamic
instability of nanoparticles requires stabilizers to generate
and maintain nanoparticle size either through electrostatic
and/or steric effects. In the current study, Naproxen was
used as a model compound and stabilizers (Lutrol F68,
Methocel E6, Kollidon VA64 and Polysorbate 80) were
evaluated to determine which were effective in producing
and maintaining stable nanoparticles. The nanosuspensions
were characterized by Dynamic Light Scattering, SEM,
HPLC, DSC and XRPD to determine physical and
chemical properties such as size, zeta
potential, shape, solubility, and chemical
and physical stability.
Experimental
combining the sodium salt of naproxen and 2.0%, 0.6%,

0.3%, or 0.1% (w/v) stabilizer solution. Yittria-Stabilized
Zirconium Beads (0.8 mm) were added and suspensions
were wet milled at 100 rpm for 5 days.
using Dynamic Light Scattering. A 20 mL aliquot of each

nanosuspension was diluted with filtered (Nylon Acrodisc
Syringe Filter (0.1 mm pore size) Nanopure water for
particles size analysis or stabilizer solution for zeta
potential analysis.
Scanning Electron Microscope. SEM samples were

prepared by collecting nanoparticles by centrifugation,
dried at R.T., and mounted on aluminum stubs using
conductive adhesive tabs. Samples were sputter coated with
gold prior to analysis.
was determined by adding excess naproxen to each solution

and rotating vials at R.T. for 3 days. Suspensions were
filtered, dilutedand analyzed by HPLC.
Conclusion
the most effective in producing and

maintaining naproxen nanoparticles at
or below 200 nm and SEM results was
consistent with particle size data.
nanosuspensions with no significant

change in crystal form or chemical
interaction with stabilizers.
that stabilization of nanoparticles by

Methocel E6 occurs via steric effects,
while Kollidon VA64 works through
steric and electrostatic effects.
References/Acknowledgments
• B.E. Rabinow. Nature Reviews Drug Discovery,
2004, 3, p 785-796.
• E. Merisko-Liversidge & G. Liversidge.
Toxicologic Pathology. 2008, 36, 43-48.
•
http://dailymed.nlm.nih.gov/dailymed/archives/fdaDr
ugInfo.cfm?archiveid=63915
(Accessed on Oct 6, 2015)
• Funding was received from Northwest Missouri
State University Applied Research
Grant, and from the Missouri Academy of Science,
Mathematics, and Computing.
Engineering and Physics

 Fully Automated Microsphere Photolithography
o Donglin Wang, Class of 2017
 Fourier photospectroscopy of Xe@C60 through a Xe 4d resonance window: theory versus recent
experiment
o Aakash Patel, Class of 2012
 Analysis of the Rotational Structure of the [16.5] 2Σ––X 2Π3/2 Component of the Red Band of
Copper (II) Oxide using Intracavity Laser Absorption Spectroscopy
o Sirkhoo Yoon, Class of 2017
 Effects of exchange-correlation potentials on the density functional description of C60 versus C240
photoionization
o Jinwoo Choi & Eonho Chang, Class of 2016
 Ubiquitous diffraction resonances in positronium formation from fullerenes
o Anzumann Chakraborty, Class of 2017
Fully Automated Microsphere Photolithography

Donglin Wang, Chuang Qu, Edward Kinzel
Missouri Academy of Science, Mathematics, and Computing, Missouri Institute of Science and
Technology
Abstract:
Photolithography is a process of removing and keeping
photoresist by exposing and not exposing the photoresist to
the UV light. Microsphere lithography is a branch of this
category that uses self-aligned microsphere to concentrate
UV light onto the surface. Having the ability to carve
patterns onto a small surface, microsphere lithography can
be used to manufacture metasurface, which has a lot of
potential industrial application. However, the processes of
microsphere photolithography are mainly operated by hand
in lab condition. During the time in Missouri University of Preparing Samples:
Science and Technology, I developed a system that can Wash 22mm x 22mm cover glass with Isopropyl Alcohol
fully automate the process of photolithography using and Deionized Water.
Labview, an industrial standard control software. By Blow dry the cover glass with compressed air
manipulating the stepper motors and controlling the shutter, Place the slide on hot plate for 15 minutes.
I can expose samples with a array of polar coordinates and
Put the slides in spin coater and turn on the vacuum pump
exposure time. During the designing process, I also
familiarized the process of microsphere lithography. to anchor the cover glass. Run the spin coaster at 5000 rpm
for 1 minute for the photoresist to evenly deposit onto the
Microsphere Photolithography: cover glass.
5. Place the slides onto the hot plate for 90 seconds at 115
Microsphere photolithography is the process of exposing degrees Celsius.
photoresist to UV light through microsphere to produce 6. Drop 1-2 drops of 3 um diameter polystyrene
desired patterns. Photoresist is a UV light microsphere solution on each sample and wait until it’s dry.
sensitive material Shape to Coordinates Conversion
Positive photoresist- exposed areas are The first step towards automation controlled lithography is
removed to convert the given shape to polar coordinates that the
negative photoresist- only the properly program can interpret. This conversation started by drawing
exposed areas will remain.Microsphere can the shape in the circle. This simulate where the shape will
concentrate UV light to a really small fit within the radius of microsphere. Then, we use
diameter, which makes it desirable for trigonometry to calculate the exact coordinate of.
producing nano-scale patterns.Microsphere
Automation Control
can also self-align, which makes it desirable
The stepper motor used in for the stage is Standa 8MR174-
to produce uniform and repetitive patterns.
11, and the controller used is Standa 8SMC4-USB two axis
controller
The software used to program the motor is Labview
coordinates in an excel spread sheet and load into the

program when needed.Results
With an exposure time of about 0.2 and 0.1 seconds with a 405 nm
UV laser, sample was exposed consecutively to produce shape of
different letters. The feasibility of producing good, ordered arrays
shows this method is facile and can be scaled up and applied to
numerous industrial applications.
Procedure:
1.First step towards automation control is installing drivers.
This makes sure that the device communicate in the proper
way. Due to the uniqueness of Standa stepper motor, there
aren’t any NI drivers that support the motor. Therefore, I
had import the library mannually to get it moving.
2.Once I made sure that the motor functions properly, I
started to interpret how the program control the motor to
move either to certain coordinate or by certain angles. This
make sure that I know how to design custom interface.
3.After interpreting the program, I started to make changes
to the program to get the interface and functionality I
wanted. Specifically, the previous program can only move
to one coordinate once at a time. However, I designed it so
that it can execute infinite amount of coordinates at one
time. Also, I deleted unnecessary functionalities that will
not effect the result of photolithography.
4.Using previous procedures, I was able to connect the
laser shutter to the computer so that it can expose the same
sample with different time in different coordinates.
5.The last step is system optimization. Although the system
can expose one sample with given coordinates, it still had
some small problems. For example, the program itself
could not save the coordinates after being closed.
Therefore, to produce the same pattern on different
samples, users need to enter all the coordinates again.
However, I design a interface that allows user to save the
Fourier photospectroscopy of Xe@C60 through a Xe 4d resonance window:

theory versus recent experiment
Aakash B Patel and Himadri S Chakraborty
Center for Innovation and Entrepreneurship, Department of Chemistry and Physics, Northwest
Missouri
State University, Maryville, Missouri 64468, USA
version at appropriate energies where many-electron effects
Abstract
dominate, have agreed well with experiments both in low-
The photoionization cross section of endohedral Xe@C60 energy plasmonic [8, 9] and highenergy oscillatory [10]
over a Xe 4d giant resonance energy region, calculated in regions for free C60. Subsequently, this method is extended
the time-dependent local density approximation, is for the SP of endohedral compounds [11]. Results have
compared with recent measurements (Kilcoyne et al 2010 shown that a novel and unusual analysis approach, Fourier
Phys. Rev. Lett. 105 213001). An analysis based on the photospectroscopy, based on the Fourier transforms of the
oscillatory cross section of any arbitrary level of the
Fourier transforms of oscillatory cross sections is
compound, identifies frequency information as unique
performed to derive a number of inherent similarities
fingerprints of the emitting level [12].
between the prediction and the data, including a large
beating-type oscillation and several others of intermediate Very recently, the first measurement of
size. Results stress the need for more accurate oscillations in the double photoionization (DP) of Xe@C60
measurements to access the wealth of information about the + over the Xe 4d giant resonance region is made [13].
geometry of the system. Since the ionizationat these energies is completely
dominated by the Xe 4d channel, the range offers a very
(Some figures in this article are in colour only in the
special energy window to test the predicted interference
electronic version). between direct and reflected 4d electrons by transforming
the signal to the reciprocal space. From the lowest order
Atoms and molecules have been successfully entrapped in many-body diagram, there are two steps leading to DP: (i)
stable and hollow carbon fullerenes, producing the an ultraviolet photon of energy E transfers a bound electron
endohedral fullerene compounds [1]. The response of these to the continuum of momentum _k, causing the SP process;
materials to an external stimulus can reveal intriguing (ii) this transferring electron interacts, with a finite
quantum phenomena unknown in the world of free systems. probability, with a second bound electron, asymptotically
Of particular interest are the endohedral fullerenes with leading to two continuum electrons of momenta _k1 and
noble gas atoms [2] because these atoms are chemically too _k2. Therefore, the integrand in an expression of the DP
inert to cause any charge transfer reaction with the captor cross section becomes a product of the corresponding SP
fullerene, ensuring the atom’s central location [3]. For such matrix element and a two-body matrix element representing
compounds, the single photoionization (SP) of the central the e–e interaction [14]. This two-body term, which
atom has long been predicted to include oscillations as a mediates the momentum exchange, is expected to average
function of the photon energy [4]. For non-valence atomic out any oscillations in it as a function of E. The implication
photoemissions, these oscillations are produced from the is that the oscillations in DP will only originate from the SP
interference of the atom’s direct ionization amplitude with matrix element and, hence, will be identical to those in the
the amplitude which reflects off the C60 hull. Important degenerate
preliminary insights of the effect were obtained through
several calculations in which the confining C60 hull is SP channel, albeit with some possible differences in their
modelled by static potentials, such as zero-width delta- amplitudes and phase.
function potential [5] or finite-width squarewell potential The prime motivation of this work is to identify the
[6, 7]. However, in either approach, C60 electrons are similarities and differences between SP theory and DP
completely omitted. Moreover, in the squarewell model, the measurements [13], and thereby to generate impetus for
width and depth of the potential can in principle be further experiments and more refined calculations. We
arbitrarily chosen as long as they together produce the show that the measured data reproduce almost all
measured C60 electron affinity, giving the potential a semi- theoretical Fourier features (oscillation frequencies).
empirical quality. However, there exist additional structures in the data, going
On a separate front, another class of calculations beyond the prediction, from various possible reasons that
has emerged which models C60 in a more sophisticated we also comment on. The details of the theoretical
local density approximation (LDA). This approach methodology for the SP process are already published [8,
determines the ground state structure of delocalized 12]. Here we provide a rather succinct account. The ground
electron cloud, formed by the valence electrons of 60 state of C60 is constructed using a LDA in a spherical
carbon atoms, moving in a jellium background of frame by delocalizing four valence electrons (2s22p2) from
equivalent positive charge [8]. SP results emanated from each carbon atom against 60 C4+ ions smeared into a
this LDA method, and from its time-dependent (TDLDA) jellium. Calculations determine the inner and outer radii of
C60 as Ri = 2.79 °A and Ro = 4.29 A°, agreeing well with
the experiment [10]. We place the Xe atom at the centre of The TDLDA cross sections, for both free Xe and
C60 and obtain the ground state of the combined system. the Xe@C60 neutral, are compared in figure 1(a) with the
The Xe 4d photoionization amplitude,D4d , for bound-to- experimental DP measurements [13] for the Xe@C60
continuum dipole transitions 4d → kp, f , is proportional to
+ion at Xe 4d resonance energies. We have checked that at
the matrix elements as
these energies the TDLDA predictions for Xe@C60+and
Xe@C60 are practically the same. Both of the theoretical
curves in figure 1(a) were needed to be scaled by a factor of
0.1, because the experiment, being for weaker DP channel,
where the induced density δV includes, besides the dipole could only account for 10% of the Xe 4d oscillator strength
interaction, terms representing electron correlations in exhausted by
TDLDA [8]. The overlap integral in the ionization
amplitude (equation (1)) is non-vanishing only over the SP. The free Xe TDLDA result is smooth, while
highly localized central region (r < Ri ) close to the Xe oscillations are seen in both the TDLDA curve and the
atom, since the Xe 4d bound wavefunction, _4d , is zero measured data, as expected. Since our focus is on pure
elsewhere. The Xe 4d giant resonance, which appears oscillatory signals, we divide the TDLDAand the
above the 4d ionization threshold (_4d = 73.0 eV) and experimental data for the compound by, respectively, the
centres at 100 eV of photon energy (E), emerges through full and the scaled TDLDA of free Xe. These ratios are
the intrachannel interactions between the 4d dipole plotted in figure 1(b). Note that since the theoretical
channels. This interaction is strong partly because the oscillation amplitudes appear weaker, we magnify the
continuum waves _kp,f oscillate practically in-phase due to TDLDA curve by a factor which makes them easier to
their identical momentum k = √ compare. We consider the oscillations from above the 4d
SP threshold up until 136 eV of photon energy for the
2(E − _4d ) (in atomic units). following analysis. This is because an unusually tall
Quantum mechanically each radial continuum structure is seen in the measurements right above 136 eV
wave representing Xe 4d photoelectrons must have two (figure 1(b)), and also a couple of negative cross section
components: one characterizing the direct escape and the minima appear at even higher energies (figure 1(a)).
other reflecting back from the C60 hull, such that
However, the in-phase behaviour of p and f photoelectron

waves, indicated above, also ensures a ‘coherence’ in their
individual reflection process embodied by equation (2).
Therefore, in the plane wave formalism, the reflection
coefficient R for a general k can be approximated as
where V (∼1.7 au) is the average depth of the hull potential

and _ (= Ro − Ri ) denotes the width of the hull. Hence, the
4d photoamplitude (equation (1)) assumes the form
where the reflective amplitude Arefl approximately relates

to the direct amplitude The detailed
derivation of equation (4) is presented elsewhere [15]. In
equation (4), Ddir is very nearly equal to the TDLDA 4d
photoamplitude of a free Xe atom and the second term on
the right-hand side denotes the reflection-induced
oscillations in the momentum space with frequencies Di
and Do, the inner and the outer diameters of C60.
The 4d photoionization cross section, ∼|D4d |2, therefore
involves the coherent superposition of the direct and
reflective contributions in the amplitude: The exact oscillation signals that are fed as inputs into the
Fourier transformation method are obtained from equation
(5) as
inducing oscillations that originate from the terms in

equation (5) related to the reflection process.
Resulting curves are plotted in figure 2 as a function of the

momentum k. The first term in square brackets on the right-
hand-side of equation (6) is linear in reflective amplitude
and, therefore, contains oscillations with frequencies Di
and Do.
The quadratic second term should carry, on the other hand,
four frequencies (from the coherent mixing of Di and Do),
which are 2_ (= Do − Di ), 2Di, 2D (= Do + Di ) and
2Do.As already known [15, 12], for energies far from the
ionization threshold, in particular for k >
√V = 1.3 au, the quadratic contribution quickly dies out
with increasing k (see equation (3)), leading to
predominantly two frequency signatures from the linear
term. However, given the momentum window of current
interest (see figure 2), k is less than
√V up to almost half-way the k-range, keeping the quadratic
process in equation (6) also important. As identified in
figure 2, medium size oscillations with period length
roughly comparable to the inverse of the C60 average
diameter are seen in both the TDLDA and experimental
curves which obviously originate from the linear process as
indicated above. More remarkably, as an evidence of the
quadratic process, a longer beating-type period, roughly
comparable to the inverse of C60 double-width 2_, is also
identified in both of the curves in figure 2. Note, for either
type of oscillations, there exist
phase offsets between theory and experiment as, most

likely, a consequence of their SP and DP distinctions,
respectively.
This phase mismatch could also be partly from the static
polarization effect of a ‘relaxing’ C60 due to the ionization
of Xe [16]—an effect which TDLDA omits. Furthermore,
as seen in figure 2, the experimental signal also exhibits a
large number of even smaller oscillations that we will
address in the following discussions.
Complete frequency structures are obtained in figure 3
which displays the Fourier transform magnitude (FTM) of
the cross sections to the conjugate radial-coordinate space
for both
TDLDA and the experiment. The TDLDA result exhibits
two strong frequencies, Di and Do, as expected for all
energies from the linear reflective contribution. The
modulating factor
e−iV 2_k associated with the Do frequency term in equation Madjet, Center for Free-Electron Laser Science, DESY,
(4) is significant over the most part of the current energy Hamburg, which helped establish the fullerene research
window (since V ∼ 1.7 au). As a result, the TDLDA Do program at
feature in figure 3 suffers significant offset from its
NWMSU, is deeply acknowledged.
expected position.
References
This frequency modulation, in conjunction with the fact
[1] Dunsch L and Yang S 2007 Small 3 1298
that the quadratic effect is characteristically weaker than
[2] Saunders M, Jim’enez-Vázquez H A and Cross R J
the linear effect, is probably the reason why, except for the
1994
2_ and weaker 2Di frequencies, other frequencies cannot
J. Am. Chem. Soc. 116 2193
rise above the noise level of theoretical FTM.
[3] Albert V A, Sabin J R and Harris F E 2007 Int. J.
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good qualitative conformity with the TDLDA prediction. [4] Connerade J-P, Dolmatov V K and Manson S T 2000 J.
Phys.
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therein
that these fluctuations are physical. They are more likely to
[6] Domatov V K and Manson S T 2008 J. Phys. B: At.
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Opt. Phys. 42 065004 and references therein
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[8] Madjet M E, Chakraborty H S, Rost J M and Manson S
induce these quadratic features—a possibility not unlikely,
T 2008
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J. Phys. B: At. Mol. Opt. Phys. 41 105101
different. Finally, it is worth noting a relevant advantage of
[9] Scully S W J et al 2005 Phys. Rev. Lett. 94 065503
the Fourier transformation: while the ‘wrong’ oscillations
[10] Rüdel A, Hentges R, Becker U, Chakraborty H S,
can affect the general shape of FTM, each frequency
Madjet M E
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and Rost J M 2002 Phys. Rev. Lett. 89 125503
may be contaminated. In conclusion, we have shown that
[11] Madjet M E, Renger T, Hopper D E, McCune M A,
most theoretical Fourier features for the SP of Xe@C60 in
Chakraborty H S, Rost J-M and Manson S T 2010 Phys.
the Xe 4d resonance energy range are qualitatively well
Rev. A 81 013202 and references therein
reproduced by the recent
[12] Potter A, McCune M A, De R, Madjet M E and
DP measurements of Xe@C60 Chakraborty H S 2010 Phys. Rev. A 82 033201
[13] Kilcoyne A L D et al 2010 Phys. Rev. Lett. 105
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Acknowledgments
The work is supported by the US National Science
Foundation. We thank Ron Phaneuf, University of Nevada,
Reno and Alfred Müller, Justus-Liebig-Universit¨ at,
Giessen for providing their
experimental data and for comments on this work. AP is
indebted to Missouri Academy of Science, Mathematics
and
Computing, Northwest Missouri State University for
summer research supports. The collaboration with Dr M E
Analysis of the Rotational Structure of the [16.5] 2Σ––X 2Π3/2

Component of the Red Band of Copper (II) Oxide using
Intracavity Laser Absorption Spectroscopy
SirkHoo Yun, ⃰ Jack C. Harms,† and James J. O’Brien†
⃰ Missouri Academy of Science, Mathematics, and Computing, Northwest Missouri State University, Maryville,
Missouri 64468-6001 and † Department of Chemistry, University of Missouri – St. Louis, 1 University Blvd,
St. Louis, Missouri 63121-4499
Abstract
The 2Σ––X 2Π3/2 transition of CuO was studied with Intracavity Laser Absorption Spectroscopy at high reso-lution in
the region 16,405 – 16,540 cm-1. The CuO molecules were produced utilizing plasma discharge in a copper hollow
cathode with 0.630 Torr of argon as the sputter gas. Iodine spectrum was collected after each plasma spec-trum. The
Iodine Atlas of S. Gerstenkorn was used to calibrate the iodine spectra and the calibrations from the io-dine spectra
were transferred to the plasma spectra. Branches in the 0-0 band of 2Σ––X 2Π3/2 transition were observed and
rotationally analyzed with PGOPHER12. With this analysis of the plasma spectra, the rotational energy levels of the
branch RQ21 were reassigned and the certainty of the molecular constants were improved by at least an order of
magnitude. This resulted from the increased accuracy and improved resolution of the data collected compared with
the work of Appelblad et al2. in 1974.
Introduction Rotational structure of an electronic transition is

The spectroscopy of metal containing diatomic understood with the selection rules that indicate the
molecules is studied in order to better understand pos-sible changes in the rotational level: ΔJ = 0, ±1.
what happens to the metal atomic orbitals when Such se-lection rules limit what transitions will be
atoms combine to form molecules. The electronic observed. For rotational energy level changes, the
spectrum of CuO has a complex structure which is rotational branches are labeled as P, Q, and R
composed of many band sys-tems.1 Due to such according to whether J changes by -1, 0, or +1,
complex structure, various interpreta-tions of the respectively. The rotational levels are fur-ther split
spectra have been made by researchers. Im- into two levels by either spin-rotation or orbital-
provements in such analyses provide benchmarks for rotation coupling, which are labeled e and f,
comparison with computational results so that the respectively. The further selection rules are that Q
compu-tational chemists can improve their branch transitions are from either e to f or f to e,
calculations for dia-tomic molecules.1, 2, 3 whereas R and P branches go from either e to e or f to
Transitions from one energy level to another oc-cur f. All of these transitions (i.e., electronic combined
when the energy of the absorbed photon corresponds with vibrational combined with ro-tational) are
to a difference between two energy levels. Visible detected based on the absorption wavelength that are
light has enough energy to cause electronic observed with Intracavity Laser Absorption Spec-
rearrangement in molecules. Along with such troscopy (ILS). By analyzing the spectra, P, Q, and R
rearrangement, rotational structure as well as branches can be identified and based on the
vibrational structure can be observed using high identification, the molecular parameters for the
resolution spectroscopy. electronic states in-volved in the transition can be
The energy level expression [1] for the studies determined. Other selec-tion rules limit the particular
involved in this research is: rotational branches that are observed and these
E (J) = Tv + Bv J (J+1) – Dv J2 (J+1)2 [1] depend on the symmetries of the mo-lecular orbitals
where J is the quantum number associated with the involved in the transition.
rota-tional level in a given electronic state, Tv is the The red band, from 580 nm to 640 nm, is a spe-cific
total elec-tronic energy change, Bv is the rotational part of the CuO electronic spectrum4. The red band of
constant, and Dv is the centrifugal distortion constant. CuO has been studied by Appelblad et al.2, Lefebvre
This research has one of its goals on determining et al.1, 5, and Steimle et al.3. The most comprehensive
these molecular constants with better certainty study was conducted in 1974 by Appelblad et al.2
compared to the corresponding pa-rameters of They ana-lyzed the rotational structures of a blue
Appelblad et al.2 band system and a red band system. In 1977,
Lefebvre et al.1 identified the 2 A′2Σ+–X 2Πi transition Utilization of ILS with a dye laser system has been
within the red band and analyzed the rotational extensively elaborated in previous publications.6, 7, 8 A
structure of the band system. In Appelblad et al.2, the schematic of this ILS system is shown in Figure 1.
excited state was assigned arbitrarily as 2Σ+. The molecular absorption spectrum of CuO was
However, Lefebvre et al.1 in 1977 suggested 2Σ– as measured us-ing ILS at Doppler-limited resolution
the ex-cited state and proved this reassignment in (~0.002 cm-1). The dye laser system was operated in
Lefebvre et al.5 in 1982. In 1986, Steimle et al.3 a time-modulated way in order to amplify the
focused their study on several lines in the A2Σ––X 2Πi absorption with the laser action in the resonator
visible band system of gaseous CuO using an cavity.6 The amplification occurs over a pe-riod of
intermodulated fluorescence tech-nique and analyzed time called the generation time, tg. The absorption
the copper nuclear magnetic hyper-fine splitting of spectrum of intracavity species was superimposed on
the CuO transition. the spectrally broad output of the laser.6 Such a
The aim of this study is to observe the electronic method en-hances the sensitivity of the of the
transition of CuO with a higher degree of accuracy absorption measure-ment.8 This specific time period
and resolution and to determine more precisely the utilized, termed the gen-eration time, tg, was directly
molecular constants associated with this transition. In related to the effective path-length used for the
1974, Ap-pelblad et al.2 studied the emission for the absorption measurement. Synchro-nized operation of
red band of CuO using photographic plate spectra in two acousto-optic modulators (AOM1, AOM2) set
the region 400 nm to 650 nm. They used a hollow the generation time as explained below.
cathode generated with a mixture of argon and The observed transmittance at a particular fre-
oxygen.2 The most favorable con-ditions for quency, Iobs (v), is related to tg via the Beer-Lambert
obtaining the CuO bands were found to be a pressure rela-tionship for ILS8:
of 0.5 Torr and discharge current of 0.3 A; these are Iobs (v) = I0 (v) exp[–σ (v) N (l / L) c tg]. [2]
almost identical to our conditions.2 Unlike our re- In this equation8, I0 (v) represents the intensity of the
search which utilized iodine spectra for calibration, laser in the absence of absorption and indicates the
Ap-pelblad et al. used a series of atomic lines 100% trans-mittance level, σ (v) is the absorption
observed from an iron arc, an iron hollow cathode, a cross section, N is the number density for the
thorium hollow cathode, and wavelengths from MIT intracavity absorber, l / L is the fraction of the laser
tables for compari-son.2 cavity of length L, 1.1 m in this re-search, occupied
This research specifically studies the rotational by the absorber, and c is the speed of light.8 In
structure of the red band in the electronic spectrum of equation [2], (l / L) c tg is the effective absorption
CuO using ILS. ILS is a technique for highly pathlength8, Leff, or 0.545 – 1.2 km for the two
sensitive spectroscopic measurements and has been generation times used.
utilized exten-sively in our laboratory. Specifics The ILS system used in this study was pumped with a
about this equipment are further explained in Pump Laser, a Coherent Verdi-V10 laser. This la-ser
associated publications (e.g., Leung et al.6, Harms et has a 532 nm output and its power range is 0.0 – 10.0
al.7, O’Brien et al.8). In this re-search, a dye laser W. The Verdi-V10 was operated with 2 W of power
system is utilized to obtain the spectra of CuO which in this research. The laser was constantly cooled by
are created in a discharge plasma in a cop-per hollow cold wa-ter. A 3-mirror cavity – High Reflector
cathode, which is within the resonator of the dye (HR), Fold Mirror (FM), and Output Coupler (OC) –
laser system. With the dye laser system, the absorp- dye laser system was utilized in this research. The
tion spectrum of the intracavity species was amplified components of this system are two short-radius
and superimposed on the spectrally broad output of curved mirrors (HR and FM) with a folded geometry
laser by operating the dye laser in a time-modulated and a flat OC.10 The output coupler re-flects 97 ~
way.6 The re-gion of interest is 16,405 – 16,540 cm-1. 98% of light and transmits 2 ~ 3% of light. This
For calibration, I2 absorption lines were recorded via system is extensively explained by Hollberg.10 The
an extracavity iodine cell. The Iodine Atlas of S. pump beam was focused onto a dye jet by a curved
Gerstenkorn was utilized as reference positions for pump mirror and then the laser was reflected in
the I2 lines.9 between the two curved mirrors.10 The energized dye
Differences in the branch assignments, band heads, was used as the gain medium in this system. The
constants, and accuracy were observed compared to wavelength of the laser was tuned with an optically
those of Appelblad et al.2 The improved accuracy of transparent wedge that disperses light as a function of
this research enhanced the accuracy of the data wavelength. Vertical and horizontal translation of the
available leading to improved molecular constants for wedge leads to variable distances for re-fraction and
the 2Σ––X 2Π3/2 system of CuO. modifies the resonant wavelength of the cav-ity,
Materials and Methods allowing for tunability. The dye we utilized in this
ex-periment as the gain media is Rhodamine 6G used as the sputter gas that hits the copper hollow
(R6G) which functions over the range of 574 – 633 cathode so that some of the copper combines with
nm. The out-put power for this dye laser system was oxygen that is either from atmosphere con-tamination
0.02 – 0.1 W. or from the surface of the cathode. No supple-mental
The transmitted light of the laser passes through the oxygen was provided in this experiment. ILS data
external iodine chamber, an acousto-optic modulator were recorded with the discharge switched on.
3 Immedi-ately afterwards the discharge was switched
off and the background spectrum was acquired. 6
(AOM2), and a McPherson 2062 monochromator. Acquisition of the background spectrum allows the
The monochromator separates the light as a function background radiation noise to be removed from the
of wave-length by rotating the diffraction grating and absorption spectrum. The noise inherent to laser
the specific wavelength to be observed is detected. cavity was reduced by placing high frequency
The generation time was obtained by the sequential buzzers in contact with the folded mirror and the dye
operation of two acousto-optic modulators, AOM1 jet. Dividing the dark-current corrected data spec-
trum with the dark-current corrected background
and AOM2, which acted as gates for the laser
spec-trum provides the spectrum for CuO.8 Then the
beams.8 Modulated utilization of AOM1, which spectral output from the laser passes through a
controlled the pump laser pulse to a 140 container filled with iodine gas, from which the
microseconds cycle, allowed the amount of pump iodine spectrum for cali-bration was acquired.
power directed into the dye jet to be alternatively The resulting iodine spectrum was calibrated with the
above (during a period of time just longer than tg) for Iodine Atlas of S. Gerstenkorn.9 Peak positions were
135 microseconds and below (for a relatively short determined from the zero crossing-points of the first
derivative spectra using Savizky-Golay polynomial
“off” period) the thresh-old value required for laser
smoothing.7 This procedure resulted in an accuracy of
action.11 For a time period of tg, AOM2 was switched better than ±0.003 cm-1. Analysis of the spectra is
off and for a certain time period, AOM2 was done using ANEW.EXE, a custom made Visual
switched on for the viewing window so that the ILS BASIC pro-gram developed and utilized in this lab.
laser beam can be detected. Then AOM2 was closed After calibration was complete, patterns in the
again. At the selected tg value, AOM2 diverted ~70 % rotational energy levels were identified. Final
of the dye laser into a high-resolution spectrograph at assignment was achieved by calculating the
a shorter time period than tg.11 The dispersed light combinational differ-ences among the branches based
that excited the spectrograph was focused onto the on the molecular con-stants from Appelblad et al.2
1024 chan-nels of diode-array detector.11 This The assignment was con-firmed using PGOPHER12,
sequence was re-peated at a rate of ~5.2 kHz and the a program used to analyze the experimental spectra.
spectral data were
accumulated for 3 or 10
scans using a
multichannel analyzer.11
A discharge plasma was formed in a 2-inch-long

copper hollow cathode within the resonator of the
dye la-ser system with a set pressure of 0.630 Torr of
argon. The copper hollow cathode is shown in Figure Results
2. The argon gas was directed into the vacuum By using the ILS system, plasma spectra of CuO in
chamber containing the hollow cathode using a Mass the region 16,405 – 16,540 cm-1 have been obtained
Flow Controller. The vac-uum chamber was in increments of approximately 7 cm-1. With argon
evacuated with an Edwards 8 E2M8 Two Stage gas at a set pressure of 0.63 Torr, a plasma discharge
Vacuum Pump. Gas pressure was measured with a 10 was created within the copper cathode at various
Torr Full Scaled MKS Baratron Capacitance discharge currents: 0.22, 0.30, and 0.40 A. At each
Manometer. Argon within the copper hollow cathode monochromator position, a plasma spectrum,
was charged with a radio pulse generator (RPG) background spectrum, and iodine spectrum were
operated at a specific current range (0.22 – 0.40 A). obtained. In total, 79 series of spectra of different
The discharge plasma was created with an ENI RPG- monochromator positions were collected and an-
50 plasma genera-tor. In this research, argon was alyzed throughout the research. After all of the
spectra were obtained, the iodine spectra were band to contain band heads for the branches SR21,
calibrated with a program, ANEW.EXE, written by RQ21, and R1 based on the work of Antić-Jovanović et
Dr. James J. O’Brien. Figure 3 provides an example
al.14. We also detected band heads for the branches
of calibrated and uncali-brated iodine spectra. The
SR21, RQ21 and R1. There are slight differences
calibration obtained from the iodine spectrum was
applied to the corresponding plasma spectrum. Figure between the band heads of this research and those
4 shows an overlay of iodine and plasma spectra at a of Appelblad et al.2 The certainty of the band head
band head of the electronic transition. Figure 5 shows positions as obtained in our research was improved
the calibrated plasma absorption spectrum for the
16500 – 16538 cm-1 region which is a composite of con-siderably as shown in Table 1.
spec-tra taken at five monochromator positions.
The calibrated plasma spectra were analyzed to
identify the rotational branches of the electronic
transition. The line positions of the identified
branches were input into an Excel file. The increment
of the differences be-tween the adjacent line positions
were calculated and uti-lized to confirm the branch
assignment from the plasma spectra. Figure 6 shows
the differences between adjacent line positions of
branch SR21 on a linear graph. Each point represents
the difference of two adjacent line positions in the
identified branch. The atomic lines in the plasma According to Appelblad et al.2, there are six branches
spec-tra were identified with NIST Atomic Spectra in the 2Σ––X 2Π3/2 sub-band: SR21, RQ21, R1, QP21, Q1,
and P1. However, since the excited state was
Database.13
corrected to 2Σ– as suggested by Y. Lefebvre et al.5,
QP21 is now QP12 and P1 is now P2. Among these six
branches, the strongest ones were the main branches
R1, Q1, and P2 in Appelblad et al.2, whereas the most
intense branches were SR21, Q1, and P2 in our
research. The rotational level diagram for a 2Σ––X
2Π3/2 transition is shown in Figure 7.2 Both the 0-0
and 1-1 vibrational bands were detected among our
ob-served spectra. All the six branches in the 0-0
band were detected in our experimental data.
However, only SR21 branch was detected in the 1-1
vibrational band so far. Many more line positions and
branches remain unas-
signed in the collected spectra. It is expected that
addi-tional lines can be observed for the 1-1 and 2-2
bands once additional laser spectra have been
acquired.
Then the determined rotational energy levels were

used to label the branches found from the plasma
spectra based on the six branches shown in
Appelblad et al.2 Combina-tion differences between
two branches were calculated and were utilized to
The identified branches were further analyzed based
secure the rotational assignments of the branches
on the work of Appelblad et al.2 The band heads in
by matching the separation between rota-tional
the 0-0 band of 2Σ––X 2Π3/2 transition detected in our
levels of the ground state as calculated from the
re-search and those in Appelblad et al.2 are
constants of Appelblad et al.2. The labeled branches
compared in Ta-ble 1. Appelblad et al.2 found this
of the 0-0 band of the

2Σ––X 2Π3/2 system
with their energy lev-

els, J, assigned are
presented in Table 2
in Appendix.
Branches SR21, RQ21,
R1, QP12, and Q1 of the
0-0 band were well
determined based on Discussion
the combinational The overall accuracy of the data of the 0-0 band of
differences. the 2Σ––X 2Π3/2 transition of CuO was improved from
±0.05cm-1 in the Appelblad et al. study to ±0.003cm-1
Proper energy levels
in our study by utilizing ILS. All of the six branches,
were not assigned for
SR21, RQ21, R1, QP12, Q1, and P2, were detected from
branch P2 of the 0-0
band until the plasma spectra. Branch SR21 of the 1-1 band in this
PGOPHER12 was transition was observed in addition from the plasma
utilized. Only after spectra. However, further research is required to
fitting the branches SR21, RQ21, R1, QP12, and Q1 with analyze this branch in depth. Moreover, more line
PGO-PHER12, the energy levels for P2 were predicted
positions for the branches of the 0-0 band are
and as-signed.
The rotational energy levels of branches SR21, R1, expected to be detected if additional spectra are
QP12, P2, and Q1 were same as those of the branches collected at higher discharge currents.
deter-mined in Appelblad et al.2 However, the
rotational energy level assignment of the branch RQ21 Interpretations of the band head of RQ21 were dif-
were different from that of Appelblad et al.2 ferent between Appelblad et al.2 and this research:
Appelblad et al.2 found that the line positions of the Ap-pelblad et al.2 analyzed the branch RQ21 to be
higher energy levels to be more in-tense in their coming out of the band head, whereas our research
emission experiment while in our analysis we found suggests that the branch is going into the band head.
that the line positions of the lower energy levels are Such analysis was based on the fact that more intense
more intense in our absorption experiment. Interpre- line positions of branch RQ21 were due to the lower
tations of RQ21 band head between Appelblad et al. rotational energy levels in this experiment. Moreover,
and our research were different. Appelblad et al. the rotational energy level assignment changed for
predicted the branch RQ21 to come out of the band the branch RQ21 from Appelblad et al.2 PGOPHER12
head by interpreting that the intense line positions was utilized to calculate the molecu-lar constants of
were coming out of the bandhead.2 However, our the rotational structure. The determined molecular
analysis of the data showed that the branch RQ21 is constants had at least one more significant fig-ure
actually going into the band head. Our analysis on compare to those of Appelblad et al.2 This improve-
this branch was based on 13 line positions, which is ment is based on the overall improvement in the
significantly less than 43 line positions in Ap-pelblad accuracy 7
et al.2 This difference is possibly due to the dif-ferent
methods utilized to record spectra between our re-
search and Appelblad et al.2: our research used
absorption spectra while Appelblad et al.2 utilized
emission spectra.
The current number of line positions for each branch
are shown in Table 3. Collection of data at higher
discharge currents would likely lead to observation of
ad-ditional lines for each branch.
of our observation and the higher resolution for our 3T. C. Steimle and Y. Azuma; An Intermodulated
study. The value of Dv x 106 turned out to be Fluo-rescence Study of the A2Σ––X 2Πi Band System
significantly differ-ent from that of Appelblad et al.2 of Cop-per Monoxide. Journal of Molecular
Additionally, the param-eter a was not needed to
Spectroscopy. 118 (1986) 237-247.
obtain a satisfactory fit of the experimental data.
Overall, this research improved on the work of 4A. Gunstch; Vibrational Levels in the Red CuO-
Appelblad et al.2 and gave a better understanding of Bands. Nature. 157 (1946) 662-663.
the red band of CuO. However, further studies are 5Y. Lefebvre, B. Pinchemel, J. M. Delaval, and J.
needed to complete the analyses for the 0-0 band, and Schamps; Laser Induced Fluorescence of an Ifrared
Y2Σ+–X 2Πi Transition of CuO: Interpretation of the
to extend it to the 1-1 band, and possibly the 2-2 X 2Πi Ground State Λ-Type Doubling. Physica
band. Scripta. 25 (1982) 329-332.
6J. W. –H. Leung, J. Ye, A. S. –C. Cheung, K. D.
Acknowledgements Gibbs, D. L. Palmer, L. C. O’Brien, and J. J.
This research would not have been possible without O’Brien; Spectros-copy of Nickel Chloride:
the help Dr. James O’Brien and his graduated stu- Identification of the [15.0] 2Δ5/2 states. Journal of
dent Jack Harms gave me. I would like to thank them Molecular Spectroscopy. 238 (2006) 54-60.
for the support and help they gave me. They led me 7J. C. Harms, C. N. Gipson, E. M. Grames, J. J.
through-out the research and taught me about basic O’Brien, and L. C. O’Brien; The Near-infrared
physical chem-istry concepts, utilization of the Spectrum of NiCl: Analysis of Vibrational
equipment, and writing papers. This research Components of System G and System H Between
convinced me to further study phys-ical chemistry. 12,500 cm-1 and 13,750 cm-1. Jour-nal of Molecular
I would also like to thank my advisor, Mr. Jo-seph Spectroscopy. 321 (2016) 78-81.
W. Meisel, who assisted me with writing this paper. 8L. C. O’Brien, K. M. Homann, T. L. Kellerman, and
Furthermore, I would like to thank Dr. Kenneth J. J. O’Brien; Fourier Transform and Intracavity
Mares, Dr. Charles Granger, and other Students and Laser Spectroscopy of NiCl System H: Identification
Teachers As Research Scientists (STARS) staff of a [12.3] 2Σ+ State. Journal of Molecular
members who pro-vided the lectures and this research Spectroscopy. 211 (2002) 93-98.
opportunity. 9S. Gerstenkorn, J. Verges, and J. Chevillard; Atlas
I would like to thank all the institutions and uni- du Spectre d’Absorption de la Molecule d’Iode
versities that provided research opportunities and 16,208-16,907 cm-1. Laboratoire Aimé Cotton, CNRS
II, Orsay (France), 1982.
lectures to the STARS students: University of
10L. Hollberg; CW Dye Lasers. In: F. J. Duarte. Dye
Missouri in St. Louis, Washington University in St. La-ser Principles: With Applications. Boulder (CO):
Louis, St. Louis Uni-versity, Confluence Life Na-tional Institute of Standards and Technology
Sciences, and Donald Danforth Plant Science Center. (1990) 190-203.
I would also like to thank the STARS sponsors: 11L. C. O’Brien, H. Cao, and J. J. O’Brien; Molecular
Office of the Chancellor-UMSL, St. Louis Constants for the v = 0, b1ΣE+gxcited State of O2: Im-
Symphony, DuPont Nutrition and Health, St. Louis proved Values Derived from Measurements of the
Oxy-gen A-Band Using Intracavity Laser
Zoo, Monsanto Company, Academy of Science of St.
Spectroscopy. Jour-nal of Molecular Spectroscopy.
Louis, Easter Seals Midwest, St. Louis Children's 207 (2001) 99-103.
Hospi-tal, UMKC School of Medicine, Missouri 12 C. M. Western; PGOPHER (Program for
Botanical Gar-den, and BioSTL. Rotational, Vibrational, and Electronic Spectra).
University of Bris-tol, http://pgopher.chm.bris.ac.uk.
References 13NIST (National Institute of Standards and Technol-
1Y. Lefebvre, B. Pinchemel, and J. Schamps; ogy); Atomic Spectra Database Line Form. National
Rotational Analysis of a Red A′2Σ+–X 2Πi System of In-stitute of Standards and Technology, http://phys-
CuO. Journal of Molecular Spectroscopy. 68 (1977) ics.nist.gov/PhysRefData/ASD/lines_form.html
81-88.
14A. Antić-Jovanović, D. S. Pésić, and G. Gaydon;
2O. Appelblad and A. Lagerqvist; The Spectrum of
CuO: Rotational Analysis of Some Blue and Red The Spectrum of CuO: Study of the Orange-Red
Bands. Phys-ica Scripta. 10 (1974) 307-324. System by use of 18O. Proc. Roy. Soc. A307 (1968)
399.
Effects of exchange-correlation potentials on the density functional

description of C60 versus C240 photoionization
Jinwoo Choi,1 EonHo Chang,1 Dylan M. Anstine,1 Mohamed El-Amine Madjet,2 and Himadri
S. Chakraborty1, ∗ 1Department of Natural Sciences, D.L. Hubbard Center for Innovation and
Entrepreneurship, Northwest Missouri State University, Maryville, Missouri 64468, USA 2Qatar
Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation,
P.O Box 5825, Doha, Qatar (Dated: October 4, 2016)
ABSTRACT
We study the photoionization properties of the C60 versus C240 molecule in a spherical jellium frame of density functional
method. Two different approximations to the exchange-correlation (xc) functional are used: (i) The Gunnerson-Lundqvist
parametrization [Phys. Rev. B 13, 4274 (1976)] with an explicit correction for the electron self-interaction (SIC) and (ii) a
gradient-dependent augmentation of (i) by using the van Leeuwen and Baerends model potential [Phys. Rev. A 49, 2421 (1994)],
in lieu of SIC, to implicitly restore electrons’ asymptotic properties. Ground state results from the two schemes for both
molecules show differences in the shapes of mean-field potentials and bound-level properties. The choice of a xc scheme also
significantly alters the dipole singlephotoionization cross sections obtained by an ab initio method that incorporates linear-
response dynamical correlations. Differences in the structures and ionization responses between C60 and C240 uncover the effect
of molecular size on the underlying physics. Analysis indicates that the collective plasmon resonances with the gradient-based
xc-option produce results noticeably closer to the experimental data available for C60.
INTRODUCTION plasmon excitation energies. These photons with their

shorter wavelengths begin to resolve the fullerene
Fullerene molecules are a highly stable form of nanoscopic molecular geometry, entering the spectral region of
carbon allotrope that can exist at room temperature. photoelectron diffraction. This effect results into the
Therefore, they are routinely attractive candidates for occurrence of a series of cavity minima observed in the
spectroscopic studies in understanding aspects of ionization spectra as the integer multiples of the
fundamental physics both in their vapor and condensed photoelectron half wavelength fit the molecular redii at
matter phases. Technologically also, fullerenes hold the certain energies [10]. The effect also accompanies a beating
prospect of exciting applications in solid state quantum modulation in the ionization spectra as a signature of C60
computations [1, 2], improving the superconducting ability molecular width [11]. Emission delay spectroscopy
of materials [3], biomedical fields [4], contrast- predicted structures at these minima [12].
enhancement research for magnetic resonance imaging
Since the first observation of C60 giant plasmon
(MRI), and improving organic photovoltaic devices [5].
resonance [13], theoretical studies with various levels of
Therefore, investigations of the response of these materials
approximation and success formed a large body of
to radiations are valuable. One direction of these studies is
published research, an account of which up until 2008 can
to understand the collective response of fullerene electrons
be found in Ref. [14]. After 2008, there have been mainly
to relatively low-energy photons. In an infinite system like
two lines of theoretical calculations that attempted to
graphite, the incoming oscillatory electric field induces
account for the atomistic details of the fullerene carbon-
plane-wave type plasma oscillations in the electron cloud
core on a truncated icosahedral geometry. One involves the
within the system’s translational symmetry. This can only
geometric optimization of the C60 structure by the
quantize a surface plasmon quasi-particle, but not the
commercially available DMol3 software followed by the
longitudinal (compressional) volume plasmon, since light is
calculation of Kohn-Sham ground state and then its linear
a transverse wave. But when the medium has a boundary,
response to the incoming radiation [15]. The other uses the
the broken translational symmetry enables the plasma wave
general access OCTOPUS software to directly solve the
to reflect and induce other eigen modes of oscillations,
time-dependent density functional equations for excited
including the volume quantization. In particular, for finite
systems with boundaries in all directions, such as fullerenes C60 to subsequently Fourier transform the density
and metallic nanoclusters, photospectroscopy reveals multi- fluctuation to obtain the dynamical structure factor utilized
∗ himadri@nwmissouri.edu ple plasmons that were to derive the electron energy-loss signal [16]. However, in
measured [6, 7]. The photoelectron angular distribution spite of these important new developments, the jellium
asymmetry [8] and the emission time delay [9] at the approximation to C4+ ion-core, a model based on which
surface plasmon of C60 also predicted interesting we have developed a linear-response density functional
behaviors. The other direction of fullerene studies involves methodology known as the time-dependent local density
the response to photons whose energy is higher than the approximation (TDLDA), has seen a significant range of
success over last several years and continues to remain (subsection B) photoemissions, as well as a comparisons
relevant [17]. This is because of the ease and transparency with available measurements for
of this model to capture the primary, robust observable
C60 (subsection C). Conclusions are presented in Section
effects and to access the key physics that underpins the
IV.
photo-dynamics and related spectroscopy.
Let us cite two sets of results from our methods that
directly connected the experiments: (i) Our calculations ESSENTIALS IN THE METHOD
have predicted the photoionization of a second plasmon at a
higher energy whose first observation was reported in our
joint publications [6, 18] with the experimental group for A. LDA exchange-correlation functionals
gas phase C60 anions; a subsequent experiment accessed The details of the method follow the framework as
this new plasmon even for the neutral C60 [19]. (ii) described in Ref. [14]. The jellium potentials, Vjel(r),
Another experiment-theory joint study of ours revealed representing 60 and 240 C4+ ions, respectively for C60 and
oscillations in C60 valence photoemissions providing trains C240, are constructed by smearing the total positive charge
of diffraction minima mentioned above [10]. over spherical shells with radius R and thickness
Besides these pivotal results, our jellium-based study also _. R is taken to be the known radius of each molecule:
extended to the photoionization of several atomic
endofullerene molecules [20–24] and the C60@C240 3.54 °A for C60 and 7.14 °A for C240. A constant
buckyonion [25]. For some of these fullerene systems, pseudopotential V0 is added to the jellium for quantitative
TDLDA investigations of the photoemission time-delay [9, accuracy [34]. The Kohn-Sham equations for systems of
12, 26] and multitudes of resonant inter-Coulombic decay 240 and 960 electrons, made up of four valence (2s22p2)
processes [27–29] were also carried out with reasonable electrons from each carbon atom, are then solved to obtain
success. the single electron ground state orbitals in the local density
One limitation of the Kohn-Sham density approximation (LDA). The parameters V0 and
functional method is its approximate treatment of the _ are determined by requiring both charge neutrality and
electron exchange. obtaining the experimental value (for C60) and the known
This is because the exchange interaction can only be fully theoretical value (for C240) of the first ionization
treated in a non-local theory such as Hartree-Fock (HF) that thresholds. The values of _ and the binding energies of the
exactly cancels out all self-interactions, restoring correct 1/r highest occupied molecular orbital (HOMO) and
behavior at r → ∞. In most of our previous calculations HOMO-1 levels of both systems are given in Table 1.
involving C60 and its derivative endo-C60 compounds we
used a widely utilized approximate scheme [30] of Using the single-particle density ρ(r) the LDA
exchange-correlation (xc) functional augmented by an potential can be written as,
orbit-by-orbit elimination of self-interaction [31] originally
proposed by Perdew and
Zunger [32]. A different scheme is to use the
gradientcorrected xc potential of van Leeuwen and
Baerends [33] that intrinsically approximates the correct where the 2nd and 3rd terms on the right are the direct and
long distance properties. While we adopted the latter in xc components. In one scheme, VXC is parametrized
some of our most recent works, no detailed study on the directly from ρ(r) by the following formula [30]:
comparative abilities between the two schemes has yet been
made. This is the primary objective of the current work that
considers the photoionization of the fullerene molecule.
Along with C60, a larger spherical fullerene, C240, has also
been considered to further broaden the scope of the
comparison. Significant differences from the choice of the
xc treatment, both in ground and photoionization in which the first term on the right is exactly derivable by a
descriptions, are uncovered. Improved agreement of C60 variational approach from the HF exchange energy of a
plasmonic spectrum from the gradient-corrected xc uniform electron system with a uniform positively charged
approach with the measured data is found. background and the second term is the so called correlation
This paper is structured as follows. Section II includes three potential, a quantity not borne in HF formalism.
subsections: A) the description of jellium core ground state In addition, we include an appropriate correction to
structures with brief accounts of two xc parametrization eliminate unphysical electron self-interactions for the i-th
schemes, B) comparison of ground state numerical results subshell that renders the LDA potential orbital specific [31,
between two schemes and between two fullerenes, and C) 35],
the essentials of the method that incorporates electron
correlations in responding to the radiation; Section III
compares the results of the valence (subsection A) and total
larger C240. Indeed, a far denser angular momentum

manifold of π and σ energy bands are generally found for
C240 as seen for LB94 bands presented in Fig. 1(b).
This correction approximately captures the electron’s long

range properties. We use the acronym SIC to refer this
model.
The other alternative account for xc-functional that utilizes
Eq. (2) but further refines it by adding a parametrized
potential [33] in terms of the density and its gradient ∇ρ as
follows,
C. TDLDA dynamical Response
A time-dependent LDA (TDLDA) approach [14] is used to
calculate the dynamical response of the compounds to the
where β is adjustable and X = [∇ρ]/ρ4/3. This scheme, external dipole field z. In this method, the photoionization
termed as LB94, is known to have lead to a considerable cross section corresponding to a boundto-continuum dipole
improvement in the asymptotic behavior of the electron transition nℓ → kℓ′ is
when compared to the exact Kohn-Sham potentials
calculated from correlated densities. Consequently, this
model is expected to also significantly improve the quality
where the matrix element M = D + hδV i, with D being the
of both the excited and continuum spectra.
independent-particle LDA matrix element; obviously, D
solely yields the LDA cross section. Here δV represents the
B. Ground states of C60 and C240: SIC versus LB94 complex induced potential that accounts for electron
correlations. In the TDLDA, z + δV is proportional to the
We show the ground state radial potentials of C60 and induced frequency-dependent changes in the electron
C240 obtained via both SIC and LB94 in Fig. 1(b) where density [14, 28]. This change is
the SIC curves, labeled as SIC-av, are occupancyweighted
average over all the subshells. This particular shape of the
potentials earlier interpreted multiple frequencies in the
Fourier transform of the measured photoelectron spectra of
C60 [10]. Yet, note the differences in details from SIC to
LB94: (i) For C60, to retain the exact same configuration of
occupied states optimized earlier [14] based on a number of
experimental findings
[36, 37], the LB94 potential gets slightly narrower (see
Table 1) and deeper but with more widening of the wings
on either side of the shell. (ii) While these general shapes
also hold good for C240, we note the following.
In the absence of enough experimental information, C240
ground states were optimized by requiring identical widths
and similar first ionization energies (Table 1) for both SIC
and LB94. This alters some properties of occupied
configuration that includes the LB94 HOMO to be of σ where the full susceptibility χ builds the dynamical
character (a level with no radial node) 1w with a very high correlation from the LDA susceptibilities,
angular momentum ℓ = 18 as opposed to a π level (with one
node) 2m in SIC of a lower ℓ = 10 [see Fig. 1(a)]. The
direct repercussion of this change on their photoionization
cross sections will be discussed below in section III A. Fig.
1(a) illustrates the general differences, SIC versus LB94, of
some valence radial wavefunctions. (iii) Finally, the
potential depth decreases from C60 to via the matrix equation χ = χ0[1−(∂V/∂ρ)χ0]−1 involving
C240 even though the latter accommodates four times more the variation of the ground-state potential V with respect to
electrons than the former. Why does this happen? To the ground-state density ρ. The radial components of the
answer, we need to bear in mind that the effective full Green’s functions in Eq. (7) are constructed with the
regular (fL) and irregular (gL) solutions of the
radial potential also includes the angular momentum
dependent centrifugal barrier part ℓ(ℓ+1)/2r2 which varies
slower as a function of r over the C240 shell region that is
radially farther from C60, creating more “energy-room” for
homogeneous radial equation autoionizing resonances. The positions and shapes of these
resonances largely vary between two xc schemes
This happens mainly because of their significantly different
descriptions of the unoccupied excited states (that depend
on the potential’s asymptotic behavior), even though their
occupied spectra are by and large similar. In fact, it is
expected that owing to the better long-range accounts of
electronic properties, LB94 resonances are more accurate in
all current results. Neglecting these single-electron features,
where W represents the Wronskian and hL = gL + i fL. broad build-ups of the oscillator strength above 10 eV are
Obviously, TDLDA thus includes the dynamical due to the two collective plasmon resonances. The general
correlation by improving upon the mean-field LDA basis. shape of the curves is qualitatively similar between LB94
and SIC for C60 [Fig. 2(a)], largely because the HOMO
levels are of the same π symmetry in both the schemes [Fig.
1(a)]. In contrast, due to the different symmetries of
HOMO for C240 [Fig. 1(a)], the broad shapes of the LB94
and SIC curves in Fig. 2(b) noticeably differ from each
other. In all the curves, there appear some imposing
oscillation-type structures above 30 eV that somewhat
mask the second (40-eV) plasmon. Further, comparing
Fig.1(a) with (b), we note a general shift of the plasmonic
enhancements toward lower energies for larger C240
similar to the known trend in the size dependence of
plasmons in noble metal cluster studies [39].
TDLDA cross sections for HOMO-1 level are
shown in Fig. 3. Since for each fullerene the HOMO-1
level retains the same π symmetry going from SIC to LB94,
the broad shapes of the curves obtained from these
approximations compare well, barring the mismatch in
details including in the single-electron resonances. We also
note here the superposed oscillatory structures at higher
energies and the red-shift of the plasmon resonances in
C240 compared to C60 as in the case of HOMO.
Cleaner shapes of the plasmon resonances are
more readily captured in the total cross sections that we
discuss in the next subsection. We address at this point a
photoelectron diffraction-driven phenomenon that begins to
surface from the waning region of the higher energy
plasmon where the collective effect starts to weaken. An
interference between photoelectron waves, predominantly
produced at the boundaries of the fullerene shell, underpins
this process. This essentially single-electron effect is the
root cause of the oscillations seen at higher energies in
Figs. 2 and 3 that has been observed before in
photoelectron spectroscopy [10, 11] and theoretically
discussed at great lengths [40]. Following Ref. [40], one
can simply model these oscillations in a nℓ-level cross
section by
RESULTS AND DISCUSSION
A. Photoionization of valence electrons

where A is a steady energy-dependent part, ao and ai are
The photoionization cross sections of the HOMO the values of the radial bound wavefunction at inner (Ri)
level calculated in TDLDA, both in LB94 and SIC and outer (Ro) radii of the fullerene shell, B = a2o
schemes, are presented in Fig. 2. Let us first note that the
host of narrow spikes that appears represents single- + a2i ,hi and ho are respectively proportional to the
electron derivatives of the radial potential [Fig. 1(b)] at Ro and Ri,
and_ = Ro−Ri. Obviously, the oscillations in photoelectron
momentum (k) depend on the potential shape that also fact that each of nℓ initial state orbital overlaps strongly
includes the angular momentum dependent centrifugal with all other fullerene-orbitals insures that these
barrier. Therefore, it is not surprising that the higher energy interchannel coupling matrix elements will be strong.
sub-structures in Fig. 2(a) and Fig. (3) qualitatively match Further, this also justifies the existence of both low and
between LB94 and SIC which have identical angular high energy plasmons at exactly the same energies for all
momentum symmetry. In Fig. 2(b), however, this matching the subshells for a given fullerene and implies the various
worsens. This is the consequence of increased centrifugal dipole matrix elements are “in phase” B. Total and band-
barrier from much higher angular momentum of LB94 differential cross sections Figure 4 presents the total
HOMO level 1w for C240 that obliterates the inner radius TDLDA photoionization cross sections and compares them
in the effective potential to effectuate hi = 0 in Eq. (10), with respective singleelectron
qualitatively altering the net shape of the oscillations. The
LDA results (shown only for LB94) for both the fullerenes.
details of this angular momentum effect were discussed
The sum over ℓ largely cancels out oscillations due to the
earlier [40]. We must also note in Figs. (2) and (3) that
reason discussed above (in the last paragraph of subsection
these higher energy oscillations are in general smaller for
III A) and makes the broad higher energy plasmon (HEP)
C240 as a consequence of the larger radius of this system
emerge clearly. In fact, both the plasmon resonances in
leading to higher oscillation “frequencies” in Eq. (10).
TDLDA stand out in Fig. 4 against the relatively smooth
Equation (10) unravels some further insights. LDA curves. Unlike to the lower energy plasmon (LEP)
Note that the first three oscillatory terms in this equation resonances, HEPs exhibit far weaker effects of single-
carry a constant phase shift ℓ′π, where the dipole selected electron resonances but rather long decay tails. Energy red-
final angular momentum ℓ′ = ℓ ± 1. The implication is that shifts of the resonances in C240 compared to those in C60
each of these oscillations for ionization from two are noted along with the fact that
neighboring ℓ states will be 180o out-of-phase to each
C240 plasmons are utilizing significantly higher oscillator
other [41]. However, the oscillation from ∼ aoai cos(k_) in
strength density due to its much larger electron pool to
Eq. (10) is independent of ℓ. But note that between the
collectivize. For each fullerene, significant differences in
ionization of a π and a σ electron this oscillation is roughly
the resonance widths between LB94 and SIC are also
opposite, since the product aoai is negative for a π radial
noted. Values of various resonance parameters are given in
wave, but positive for a σ – an implication of which will be
Table II.
discussed in the following subsection.
From a non-perturbative many body theory, the
emergence of plasmon resonances can be thought of as
originating from the formation of collective excited states
under the influence of external electromagnetic field [42].
Since the collective excitations are energetically embedded
in the single-electron ionization channels, they provide
alternative ionization pathways degenerate with single-
electron channels. Thus, the autoionization of these
collective excited states induce resonant enhancements in
the subshell cross sections as shown in Figs. 2 and 3.
However, from a perturbative approach the plasmon
mechanism can be best modeled by Fano’s interchannel
coupling formalism [43]. To include the effects of channel-
coupling upon the final state wave function of each of the
perturbed dipole matrix elements Mnℓ(E) one can write
[14], over the two energy regions (bands) of each fullerene
[Fig. 1(a)]. Consequently, the various terms in the sum in
Eq. (11) will add up coherently, leading to the dramatic
enhancement.
Equation (11) reveals one further important correlation
feature. Since a π (or a σ) bound orbital will have near-
perfect overlaps with other π (or σ) orbitals due to their
almost identical shape and spatial extent, the interchannel
coupling matrix element in Eq. (11) will be stronger for a
π-π or a σ-σ self-coupling than a π-σ crosscoupling.
Therefore, it is expected that the π electrons will show a
where Dnℓ is the unperturbed (LDA) nℓ matrix element, preferred participation for building LEP and the σ for HEP.
ψnℓ(E)’s are the unperturbed final continuum channel wave Figs. 5 and 6 respectively show the only-π
functions of the single-electron channels, and the sum is
over all of the photoionization channels except the nℓ
channel. The matrix element within the integral of Eq. (11)
is known as the interchannel coupling matrix element; the
with symmetric and antisymmetric vibrations between the

inner and outer surfaces suggests that the midpoint energy
between the two resonances to be about the same for C60
and C240, since they have approximately same initial
electron densities [45]. According to this model the
plasmons are then formed below and above this midpoint
energy shifted equally both ways, and this shift grows with
the increasing radius, suggesting that the plasmons will be
more separated out for C240 [45]. Clearly, that is not seen
in Fig. 4, in which both the plasmons red-shift for C240
and in fact move close to each other compared to their C60
results (see Table. II for the actual values), suggesting that
quantum effects play an important role. One possible way
to understand this phenomenon quantum mechanically is to
recall in Fig. 1(b) that the
C240 ground state potential is shallower while
accommodating a number of electrons four times that of
C60 producing far compact energy levels. This suggests a
decrease of the average ground state binding energy for
C240. Therefore, since in the spirit of Eq. (11) the
plasmons can be interpreted as the coherence in close-
packed single-electron excitations, it is only expected that
the plasmons will begin to excite at lower photon energies
causing their early onsets for C240, as seen in Fig. 4. In
fact, this trend of red-shifting plasmons with increasing
fullerene size should be rather generic, at least in the
jellium based quantum calculations. An insight in the
phenomenon can be motivated by perceiving a collective
mode as having a natural oscillation frequency p κ/ρ of a
mass density (ρ) on a spring of stiffness κ [25]. Thus, a
shallower binding potential with higher electron population
for C240 translates to the loosening of the spring
decreasing κ and thereby its resonant frequencies.
Let us now compare between the predictions of LB94 and
SIC for the band-cross sections. For the π-band, LB94
retains a contribution approximately similar to that of SIC
at LEP, but shows depletion at HEP which is more
prominent for C60 [Fig. 5(a)] than C240 [Fig. 5(b)].
For the σ-band, on the other hand, a notably higher
contribution to LEP and some increase at HEP by LB94 for
both the systems are found [Fig. 6]. There are more.
Our discussions following Eq. (10) indicate that the ℓ- sum
over π or σ cross sections will significantly weaken the
diffraction oscillations coming from the first three
oscillatory terms in Eq. (10), while the fourth oscillation ∼
cos(k_) will survive being free of ℓ. As a result, in the
band-cross sections this _-dependent oscillation will
and only-σ band cross sections in TDLDA calculated in dominate. Since _ slightly shortened in LB94 than SICfor
both LB94 and SIC. For each fullerene, if we compare the C60 [Fig. 1(b)], π-band LB94 curve in Fig. 5(a) produces a
π band result in LB94 with the total cross section in LB94 longer wavelength in k to induce its first minimum above
(also shown), a dominant contribution of the π-cloud to 100 eV at an energy higher than that in SIC. The equality
LEP and of the σ-cloud to HEP are indeed noted. In of _ in LB94 versus SIC for C240, on the other hand,
general, however, it is also obvious from these comparisons justifies the occurrence of these minima at about the same
that either of LEP and HEP in a fullerene are of both π and energy as in π-band results for this fullerene [Fig. 5(b)].
σ mixed character, it is just that one is dominant on the However, this effect is not so intuitive for the σ-band case.
other. As seen, while the minimum in LB94 for C60 [Fig. 6(a)]
does appear at higher energies than the SIC minimum, they
A discussion on the red-shift of TDLDA plasmon do not seem to coincide for
resonances from C60 to C240 [Fig. 4] may now be in order.
Classical plasmon-model [44] of a spherical dielectric shell
C240 [Fig. 6(b)] as they did for C60. The latter is due to the both the fullerenes using a formula that includes two
fact that the σ states for C240, reaching very high in ℓ Lorentzian line profiles. We further present in Fig. 7, two
values compared to their counterparts in C60, produce such similar fitting curves for the SIC results of the fullerenes.
strong centrifugal repulsions that the effective potentials for For both fullerene systems, Table 2 presents the positions
high ℓ considerably deform rendering the role of _ less (Eo) and full-widths at halfmaxima (FWHM), �, and
meaningful [40]. oscillator strength densities (OSD) corresponding to each
plasmon resonances calculated in LB94 and SIC; LB94
results are displayed in parenthesis.
From Table 2 and Fig. 7, going from SIC to LB94, both
LEP and HEP of C60 move up in energy by 1 eV, while
C240 LEP by a half eV. We recall the spirit of a classical
oscillator model of dielectric shell that the plasmon
frequencies are proportional to the square-root of the ratio
of rigidity to density (p ∼ κ/ρ, in analogy to the oscillation
frequency of a mass on a spring of stiffness constant κ)
introduced in the previous subsection. Note, LB94 radial
waves being slightly more spread out than their SIC
counterparts occupy a larger space effectively decreasing
the density. This explains the blue-shift of LB94 plasmons.
This trend in LB94 is an improvement, since jellium based
prediction of C60 plasmon resonance energies are known to
be below their measured values [14]. However, this trend is
reversed for C240 HEP where LB94 moves this plasmon
lower in energy by more than 2 eV from its SIC prediction,
ascertaining the importance of quantum effects to capture
the details of these resonances. Furthermore, the LB94
width of C60
LEP is found to be 3.5 eV, which is an increase of 40%
over its SIC value of 2.5 eV, while this increase is 30% for
C60 HEP. More than a double increase of width for C240
LEP is found going from SIC to LB94, while again, this
trend reverses by a small amount for C240 HEP.
Significant variations in the OSD utilized by each plasmons
C. Plasmon resonances and comparison with experiments
for either system between two xc approximations are also
Measurements [6, 18, 19] of plasmon resonances in the noted in Table 2, accounting for the detailed differences
photoionization of neutral and ionic C60 produced that the two calculation schemes generate.
relatively smooth curves without any evidence of
Comparisons of the results between the two
autoionizing resonances, which exist in our theoretical
fullerenes in Fig. 7 as well as in Table 1 indicate a generic
TDLDA results. As discussed in details in our earlier study
red-shift of plasmon energies for the larger fullerene C240,
[14], this is likely because the coupling of electronic
as noted and discussed earlier. We also find in Table 2 a
motions
general trend of the width � to decrease with the increasing
TABLE II. Resonance positions (Eo), FWHM (�) and size of fullerene, except for C240 HEP in SIC. Further note
oscillator strength density (OSD) of the lower energy (LEP) that while for C60 LEP the OSD value increases from SIC
and the higher energy (HEP) plasmon. The values in to LB94, the trend is found opposite for this resonance of
parenthesis are corresponding LB94 results. C240. For the HEP, either fullerene exhibits decrease in
OSD going from SIC to LB94. Fig. 7 further includes two
sets of experimental measurements for C60, where the data
from Hertel et al [13] are red-shifted by 3 eV and those
from Reinköster et al [19] by 1 eV to match respectively
with the energies of LEP and HEP calculated in LB94. As
evident, the modifications in � and OSD, as brought about
by the LB94 scheme, indicate an improved agreement with
experimental results compared to what SIC achieves. We
must also note that in a jellium model, the plasmon
with the temperature-induced vibration modes of the core resonances only decay via the degenerate single-electron
[46] and the fluctuation of the cluster shape around the channels. In the real system, however, there would be
shape at absolute zero [47, 48]. In addition, the inherent additional effects from the independent local ion sites
over-delocalization of jellium models predicts autoionizing positioned based on an appropriate atomistic symmetry, at
resonances that are too narrow, as seen in our results. least for relatively more tightly bound electrons. As shown
Therefore, in Fig. 7, we fit the non-spiky background parts in detailed with
of our TDLDA total cross sections obtained via LB94 for
SIC results in Ref. [14], in order to account for these In conclusion, the work accounts for various robust
additional decay channels, the theoretical cross section in a similarities but detailed differences between the results
jellium frame must be convoluted with a small width in obtained via two standard xc schemes, SIC and LB94, in
order for a more meaningful comparison with the framework of density functional description of
measurements. delocalized valence electrons of the fullerene molecule
where the ionic core is treated as a jellium shell. The focus
With the already improved agreement of the current “zero-
has been applied to understand both the ground state and
width” results of LB94, it is only expected that such a
single-photoionization properties of the system. For the
convolution will further better the agreement with the
ionization study, the ultraviolet energy range of plasmon
experiment.
activities and above-plasmon soft x-ray range were
considered. The comparison between the results of two
CONCLUSIONS prototypical spherical fullerenes, C60 and C240, further
unravels the scopes of validity of these two theoretical
schemes. A natural next step is to
consider the influence of xc formalism on the photospectroscopy of nonspherical fullerenes, which, however, is a topic for our
future research. To this end, within the known limitation of the jellium description of the molecular ion-core, the gradient
corrected LB94 formalism seems to bring the results closer to the measurements on C60 over the plasmon resonance energy
region. We hope that with possible future experiments with C240 the success of LB94 scheme can be verified for larger fullerene
systems as well.
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Ubiquitous diffraction resonances in positronium formation from fullerenes

Paul-Antoine Hervieux,1, Anzumaan R. Chakraborty,2 and Himadri S. Chakraborty2, †
1Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg,
67000 Strasbourg, France
2Department of Natural Sciences, D.L. Hubbard Center for Innovation and Entrepreneurship,
Northwest Missouri State University, Maryville, Missouri 64468, USA
(Dated: October 4, 2016)
ABSTRACT assisted production of low-energy excited Ps is achieved in
the interaction of cold-trapped positrons with Rydberg
excited Cs atom [12].
Due to the dominant electron capture by positrons from the
However, in spite of such broad landscape of Ps research,
molecular wall and the spatial dephasing across the wall-
little attempt of Ps formation by implanting positrons in
width, a powerful diffraction effect universally underlies
nanoparticles, in gas or solid phase, has so far been made,
the positronium
except for a single theoretical study using Na clusters [36].
(Ps) formation from fullerenes. This results into trains of On the other hand, straddling the line between atoms and
resonances in the Ps formation cross section as a function condensed matters are clusters and nanostructures that not
of the positron beam energy, producing uniform structures only have hybrid properties of the two extremes, but also
in recoil momenta in analogy with classical single-slit exhibit outstanding behaviors with unusual spectroscopic
diffraction fringes in the configuration space. The effects [37]. Formation of a quasi-free electron gas within a
prediction opens a hitherto unknown avenue of Ps finite nanoscopic region of well-defined boundary, as
spectroscopy with nanomaterials. opposed to a longer-range, highly diffused Coulomb-type
boundary characteristic of atoms and molecules, is a
PACS numbers: 34.80.Lx, 36.10.Dr, 61.48.-c
property of nanosystems which ensures predominant
electron capture from localized regions in space. This may
Following the impact of positrons with matter the lead to diffraction in the capture amplitude, particularly at
formation of exotic electron-positron bound-pair, the positron energies that cannot excite plasmon modes. The Ps
positronium (Ps), is a vital process in nature. This channel formation from fullerenes can be singularly attractive to
accounts for as large as half of the positron scattering cross access this diffraction phenomenon due to fullerene’s
section from simple atoms and molecules [1], as well as an eminent symmetry and stability, and its previous track
even higher success rate of Ps formation on surfaces and record of success in spectroscopic experiments [38]. In this
thin films [2]. Other than probing structure and reaction communication, we show that the Ps formation amplitude
mechanism of matters, the Ps formation is a unique from the positron colliding with C60 does include a strong
pathway to the electron-positron annihilation process [3, 4] diffraction effect, resulting in a system of peaks in the form
with both astrophysical [5] and applied [6] interests. of broad shape resonances, in the total ground and excited
Possible production of Bose-Einstein condensate of Ps has Ps formation cross section for state-selected captures.
also been predicted [7, 8], besides the importance of Ps in The C60 molecule is modeled by smearing sixty C4+ ions
diagnosing porous materials [9] as well as in probing in a spherical jellium shell, fixed in space, with an
bound-state QED effects [10]. More- over, efficient Ps experimentally known C60 mean radius rc = 6.7 a.u. and a
formation is the precursor of the production of width determined ab initio [39]. Inclusion of molecular
dipositronium molecules [11] and antihydrogen atoms [12, orientations will have minimal effect on the result due to
13] required to study the effect of gravitational force on the C60 symmetry [40]. The delocalized system of total
antimatter [14, 15]. Theoretical investigations to calculate
240 valence electrons from sixty carbon atoms constructs
Ps formation cross sections from atomic hydrogen [16–18],
the ground state in the Kohn-Sham local-density
noble gases [19–21], and alkali metals [22, 23] are aplenty.
approximation (LDA) [39] improved by the gradient-
Calculations with molecular targets, although relatively
corrected Leeuwen and Baerends exchange-correlation
limited, include the molecular hydrogen [24], polyatomic
functional(LB94) [41].This produced bands of π (one radial
molecules [25], and the water molecule [26].
node) and σ (nodeless) states with HOMO and HOMO-1 to
Simultaneously, precision experimental techniques to
be of 7h (ℓi = 5) and 6g (ℓi = 4) π character respectively – a
measure Ps formation signals have also been achieved by
result known from the quantum chemical calculations [42]
im-pinging positrons into varieties of materials, such as,
supported by direct and inverse photoemission spectra [43],
atomic and molecular gases [27, 28], molecular solids [29],
and from energy-resolved electron-momentum density
liquids and polymers [30], zeolites [31], metal surfaces and
measurements [44]. The LDA radial ground state potential
films [32], metal-organic-frameworks [33, 34], and
and the radial HOMO wavefunction are shown in Figure 1.
mesostructures [35]. Very recently high yields of laser
Linear response type calculations using this ground state 60 interaction, after the i-th electron is captured, plus the
basis well explained mea- long-range 1/r+ interaction between them gives the positron
scattering potential, V sci (r+), from the C+
60 ion; the LDA version of this potential for a HOMO
electron capture is given in Fig. 1. 1/ρ is the Coulomb
interaction between the positron and the captured electron.
For a given electron position, Eq. (2) embodies the
snapshot amplitude for the transition of an incoming
positron to a Ps-bound outgoing positron. W(~r−;~ki) thus
provides the perturbation in Eq. (1) for the capture of the
bound electron into a moving Ps. We use Eq. (1) exactly to
compute our results, but consider simplifications to
interpret them. Integrations over 1/ρ will produce a steady
contribution S(~ki) to the amplitude in energy which we
ignore temporarily. This steady behavior may be justified
by the steady Ps formation cross section of atomic
hydrogen 1s capture into Ps(1s) [Fig. 2(a)] where V sc
i in Eq. (2) is simply replaced by 1/r+. Also, to better
explain our results, we approximate the three distorted
Coulomb continuum waves, representable by confluent
hypergeometric functions [36], in Eqs. (1) and (2) as plane
waves of the form F(−)~k(~r) _ exp(−i~k · ~r). These plane
waves can expand in spherical harmonics:
With these and assuming the capture in an nf s Ps state

φf (~ρ) _ Rnf s(ρ)Y0,0(ˆρ), Eq. (2) simplifies to
sured photoemission response of C60 at the plasmon

excitation energies [39, 45]. Similar calculations at higher
energies also supported an effective fullerene width where ~q = ~k+ −~ki is the momentum transfer vector and
accessed in the experiment [38]. Jellium-type modeling of
multiwalled carbon nanotubes also had success in Eq. (4) is isotropic in ~q. (In writing Eq. (4), we assume
describing laser pump-probe measurements [46].Consider Ps formations in the forward direction, which was found to
an incoming positron of momentum ~ki which captures an be the most dominant direction in both earlier [48] and
electron from a C60 bound state φi(~r−) to form a Ps state recent experiments [49], so that ˆr− and ˆr+ are identical
φf (~ρ). As illustrated in Fig. 1, the positron and electron and thus ~ρ is independent of ˆr+.) Adopting the same
position vectors, ~r+ and ~r− respectively, originate from simplification for F(−)_
the center of C60 so that ~ρ =~r− − ~r+, and ~k+(−) denote
positron (electron) outgoing momenta in Ps that are equal, ~k−(~r−) in Eq. (1) to apply in Eq. (3) and then combining
resulting 2~k+(−) to be the momentum of Ps itself. Since with Eq. (4), we can rewrite the full amplitude (1) for a
we access energies above C60 plasmon resonances, the capture from C60 niℓi state as,
many-body effect is not important, justifying the use of
mean-field LDA wavefunctions and potentials in the
framework of independent particle model. Therefore, the
prior form of the Ps formation amplitude can be given in
the continuum distorted-wave final-state (CDW-FS)
approximation [36, 47] as, where we used asymptotic forms of the spherical Bessel
function jℓ(r) _ sin(r − ℓπ/2)/r. We will ignore the
3 spherical harmonics in Eq. (5), since the forward
in which direction is considered. Before moving further let us note
the following in the amplitude (5) in conjunction with Fig.
1: (i) Large values of V sci only at the C60 shell indicates
the shell to be the window of appreciable repulsive
interactions of the positron with C60. (ii) The shape of the
Ps radial wavefunction Rnf s(ρ) identifies the region of
success of Ps formation as a function of electron-positron
where the short-range positron-C+ separation ρ = |~r− − ~r+| where a Ps s-state has the
maximum probability density at r− = r+. (iii) The radial
wave function of C60 i-th level r−Rniℓi ensures that

electrons must be available for the Ps to form. Considering
Ps(1s) formation from the capture off C60 HOMO level,
we took eleven electron-positions in Fig. 1 within the
interaction window around C60 radius (rc) and plot the
product R1s(ρ)V sc7h (r+)[r+R7h(r+)] of the three
quantities mentioned above; the r− values considered are
shown by dots in the same color of that of the curve it
generates. Since Ps will have a propensity to successfully
form toward ρ = 0, the curves show maxima and minima at
various locations symmetrically on the left and right side,
respectively, of rc. This opposite orientation is because of
the shape of C60 7h wavefunction which is asymmetric
about its node. It is fair to approximate that the dominant
behavior comes from the optimum positions at rp. Thus,
choosing r− = r+ = rp in Eq. (5) these contributions indicate
trains of peaks given by sin(k−r− − ℓiπ/2) sin(qr+) _
sin(Qrp − ℓiπ/2) where the recoil momentum Q = ki −2k±
for the Ps formation in the forward direction. The
amplitude A(rp) of the oscillation is proportional to the area
(r+ integral) under the corresponding bump. Hence, the
remaining r−integral in Eq. (5) can approximate to a
simpler form
Noticing that the bumps appear on either side of rc at

similar distances α (Fig. 1), Eq. (6) can be rewritten as
Since these diffraction peaks appear in the energy

(momentum) domain, we call them diffraction resonances
which must also show up in the Ps formation cross section
where the negative sign between the two terms justifies the proportional to the squared modulus of Eq. (8). Further, this
maxima and minima about rc (Fig. 1). We finally obtain squaring operation modifies the functional form of the
structures as cos(Qdc − ℓiπ) in the cross section, where dc
is the C60 diameter. Broad resonances are seen in Fig. 2(a)
for the numerical Ps(1s) formation cross section for the
captures off four C60 levels as a function of the forward-
emission recoil momentum Q corresponding to the electron
Obviously, the integral in the above equation spatially excitation energy from roughly 50 eV (above the plasmon
dephase the sin(Qα) modulation, since α varies with r−, excitation) to 270 eV (below the K-shell of atomic carbon).
retaining peaks in the amplitude only via cos(Qrc − ℓiπ/2). For a direct comparison, also presented in Fig. 2(a) is the
Here is the essence of what is going on. Within about the steady result for the atomic hydrogen target showing no
fullerene width region, a strong constructive and such resonances. The off-4 sets between the peaks for the
destructive interference take place as a function of Q. When HOMO versus HOMO-1 versus 2s (the bottom most level
the odd integer multiple of the half- wavelength of effective of C60 π band) results connect to the phase-shift ℓiπ/2 in
continuum wave as a function of Q fits the distance rp, Eq. (8) that depends on the angular symmetry of the initial
systems of peaks (bright-spots) in the energy domain are state. The shape and strength of these resonances are best
formed which subsequently results into a single centroid illustrated by considering the cross section ratios, shown in
fringe pattern via a dephasing mechanism in the integration Fig. 2(b), which neutralizes the non-resonant background
over the electron position as described above. decays, and therefore can be accessed in experiments by the
Ps formation spectroscopy with better accuracy much freer
of the experimental noise. It is important to note that we
used plane wave descriptions in our analysis to interpret the
key results. But the actual character of the resonances are
more diverse than this simple account, as seen in Fig. 2(b).
If the capture is from a C60 σ state, which has no radial
node, we still also find Eq. (7) but with a positive sign
between the two terms in the integration. This will produce
a sine function in Eq. (8) leading to cos(Qdc − ℓiπ + π)
structures in the cross section for a C60 σ electron capture.
This suggests that for the same angular momentum the π
electron capture cross section will produce 180o out-of- found (not shown) the resonances to be more compact in
phase resonances compared to a σ electron capture, as energy than C60, since C240 is a larger diffractor.
clearly seen between the HOMO and 6h results in Fig. 2(a).
In conclusion, we calculate the Ps formation cross section
This indicates that electronic structural information can
in the CDW-FS method for electron captures from various
also be accessed spectroscopically by Ps formation from
C60 levels. The C60 ground state structure is modeled by a
fullerenes.
simple but successful LDA frame. Hosts of strong and
broad shape resonances in the Ps formation are predicted.
The resonances are engendered from a diffraction effect in
the Ps formation process localized on the fullerene shell.
The effect should be universal for Ps formation from
nanosystems, including metal clusters, carbon nanotubes,
or even quantum dots that confine finite-sized electron gas.
The work ushers a new research direction to apply Ps
formation spectroscopy to gas-phase nanosystems which
we hope can begin with fullerenes, since they currently
enjoy significant attraction in precision measurements.
The research is supported by the National Science

Foundation, USA.
_ hervieux@unistra.fr
† himadri@nwmissouri.edu
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Economics
 The growth of the Consumer-driven Economy in China
o Yifei Chen, Class of 2017
The growth of the Consumer-driven Economy in China
Yifei Chen
Introduction
As the impact of the economic 2.1 Chinese change of the economic
globalization becomes stronger, a number mode
of diverse economies show up. With this In the twentieth century, in order
competing and developing environment, to develop the economics and catch up
China becomes one of those economies with other developed countries, the
entities which greatly influences Asian government of China carried out the
economies. investment-driven economy, an economic
When it comes to 21st century, model mainly motivated by the
China has already become the second government. By using this economic
biggest economic entity in the world. system, the GDP of China increased by
Chinese GDP represents 17.53% of the 7% to 12% each year on average.
whole economy in the world with a steady However, as time went by, the
annual increasing rate of about 6%-7%. In investment-driven economy could not
the second quarter of 2016, its economy strongly support the country in an
advanced with a 6.7% annual rate (China efficient way anymore. That’s the time
GDP Annual Growth Rate, 2016). This when the consumer economy was carried
dramatic economic improvement credits out and played cardinal role in the future
to the implementation of consumer-driven of China.
economy in China.
Fengqiang, the author of the article “the 2.2 A supportive potential power
characteristics and the theoretic meanings
of the consumer economy”, states that the According to “The report of the
consumer economy is type of economy trend of consumption of China----Three
model where consumption plays a leading new powers lead to the new consumption
role in the contradiction between economy”, people from the upper
production and consumption. In this bourgeois and the wealthy class in China,
economic mode, the process of production whose number is increasing rapidly, from
is hard to run without the support of current 17% to about 30% in 2020, will
consumption. Therefore, this economic lead to the advance of the consumption in
system depends more on the consumption future. In 5 years, the consumption
than on the support of the Chinese credited by the upper class will take part
government. With this economic mode, 55% of total urban consumption while
the government does not need to borrow contribute 81% of the increase of the total
tremendous amount of money from consumption. In 2020, those people’s
outside. Given all that, this special total consumption will raise at the rate of
economic system is sustainable and 17% and contribute 1,500 billion dollars.
suitable for Chinese current economic With this strong support, Chinese
situation. consuming ability as a whole will
dramatically increase. Then how will the
2.0 Background information consumption-led economy grow with this
strong support in China? The next chapter and services. Based on the figure
is going to talk about Chinese current given above, in 2015, 55% of
consuming situation. Chinese customers held an
optimistic attitude towards the
growth of their total families’
income. However, compared to
Chinese consumers, there are only
respectively 32% and 30% of the
customers from the United States
and the United Kingdom holding a
positive attitude for their future
income in 2011 (Zipser, Chen,
Gong, 2016). Therefore, Chinese
potential consuming ability is
larger than the developed country.
Source from: National bureau of statistics The positivity and optimism
of China towards the future economic
development motivates Chinese
consumers to purchase more
3.0The current consumption products, leading to the increase of
condition Chinese consumption in total.
Consequently, the consumption-
3.1 Customer confidence based economy has a large
potential market and a strong base
of supportive consumers.
3.2 Consuming variety

3.21The change in
people’s expenditure on
various products
Source from: McKinsey 2016

Chinese customers report
According to the
Investopedia.com, the consumer
confidence is an index given by
the Conference Board to measure
the optimism of the consumers
about the economy in the future. If
the index of the consumer
confidence increases, which Source from: McKinsey 2016
means that consumers are more Chinese customers report
optimistic with respect to their
country’s economic conditions,
they will consume more products
Depending on the data

given by the figure above,
compared to the data from 2012,
the number of the people who will
increase their expenditure on food
after they had better income
decreased by 30% in 2015. Also,
the number of people who will
increase their expenditure on
health products and clothes, which
are two classes of products, just
increased by 1% and 3%
respectively. However, more and
more people said that they would Source from: McKinsey 2016
increase their expenditure on worldwide customer confidence
services such as personal care report
services, travel and amusement
(Zipser, Chen, Gong, 2016). In a According to McKinsey
word, more and more people start 2016 worldwide customer
to pay attention to the services and confidence report, consumption
improve their lives quality and upgrading is in a great trend with
spend less expenditure on the strong energy, especially for the
basic products like food and high-end products such as
clothes. Now, amusement, makeups and alcohol. The upgrade
services, and expensive products of the high-end products is much
play an increasingly important role more than the basic products. This
in people’s daily lives and take up trend points out that people’s
more expenditure. As people consuming ability improves a lot
begin to spend more money on and Chinese total consumption
services and high-end products will reach a higher level. In order
which cost more money, more to catch up with the consumers’
money flows into the market tendency, the Chinese enterprises
rather than being stored in the should find out the development
bank, advancing the consumption prospect of the high-end products.
in China. This provides the Then Chinese’s market system can
consumption-led economy a better reach a higher level with the
developing space and gives a reciprocal effects between
strong support to this economic merchants and consumers.
mode.
3.22Upgrade of products
3.23 Effects of the brands strengthen the publicizing of the

importance of new brands. In this
way, Chinese consumers hold an
opener mind for new brands and
try the products from those new
enterprises. This can help
domestic brands and native
economics develop better.
3.24 Travel & Shopping
Source from: McKinsey 2016

Chinese customers report
Depending on the report

done by McKinsey in 2016, more
and more people are in the trend
of paying attention to just a few
specific brands of a product.
Customers wills to trying new
brands decrease. Now it becomes
harder for new enterprises to
attract customers while sell
products. This tendency indicates Source from: McKinsey 2016
a potential block for the Chinese customers report
consumption-led economy. Since
people only care about few brands, Based on the figure given
especially some foreign by McKinsey 2016 Chinese
international brand, the customers report, nearly half of
phenomenon of monopoly will interviewees indicates that
increase rapidly in the market and shopping plays an important roles
reduce the mobility of the market. in their trips. 79% of the
As a consequence, the interviewees do shopping during
consumption can’t efficiently the trip in holidays. This figure
develop and the consumption-led illustrates the importance of
economy in China will be blocked. shopping in people’s trips.
In order to provide a better Chinese government can exploit
economic environment for the new the potential travel areas, advance
consumer-driven economy, the the shopping systems around the
Chinese government should carry traveling areas to a high-end and
out policies to reduce the organized system, and motivate
phenomenon of monopoly in the native people to start the
market and provide resources and undertakings based on their
spaces for new enterprises to special characteristics. In this way,
grow. Also, the government can not only the cultures at the areas
are protected, but also the policies based on the new

economics is developed. economic conditions in the
market.
3.3Consumption patterns
4.0 The problems the
Consumption-led Economy in
China is facing and the
challenges
Because of the use of
consumption-led economy system,
Chinese economics becomes more active
and is in a good shape. However, even
though this system used in China is in a
Source from: McKinsey 2016 positive trend, it still meets some troubles
Chinese customers report and challenges in its way. Here is some
problems and challenges which make the
According to McKinsey 2016 consumption-based economy can’t grow
Chinese customers report, the successfully.
customers in China still have
higher degree of satisfaction of
physical stores than online ways. 4.1 Overseas consumption takes
However, the degree of off large part of Chinese people’s
satisfaction of online shops expenditure
increase rapidly, which caused the
difference between physical and
online stores decreased. Online
shopping is a noticeable way to
motivate people to consume. With
this strong support, the
consumption-led economy can
rapidly develop. As the online
shopping becomes more and more
popular, the Chinese government
should analyze, adjust, and
improve the policies about online
shopping to provide a better Source from: McKinsey 2016
environment for this new powerful Chinese customers report
economic form. Even though the According to McKinsey 2016
online shopping grow rapidly, the Chinese customers report, overseas
physical store is still a cardinal expenditure takes off 27.2% of Chinese
and necessary part of the people’s expenditure on average, which is
economics. Therefore, the the same as the expenditure on fixed
government should balance the expenditure like house rent, board
expenditure on these two expenses and so on. At this point, much
economic forms and improve the
money of Chinese flows into foreign less than 3000 dollars and the one which
market, which caused the consumption have per capita GDP between 3000 and
contribution rate slowly increasing. Also, 6000 dollars. Because Chinese
the brands that take off a large ratio in government can’t effectively improve the
Chinese market and also the ones most of social security system, many people show
the consumers aim at are often little confidence in their future security.
international foreign enterprises whose This limits people’s ability to consume,
general headquarters are in foreign which caused the consumption-led
countries. This blocks the domestic economy system can’t function well.
enterprises from developing and the 4.3 GDP increases fast but not in
currency of Chinese market. a sustainable way
The will to quickly increase the GDP
4.2 Chinese social security leads to the rough economics growth
system is not complete patterns. According to the article,
enough Challenges and solutions of Chinese
According to the Challenges and consumption-led economy growth, even
solutions of Chinese consumption-led though Chinese economics is quickly
economy growth, Chinese people do not developing, this development is
hold a positive attitude on their future’s dependent on using a lot of labor, natural
security, which made their consuming source, funds, land and some corporeal
patterns become more conservative. There production factors rather than depending
are mainly three reasons why people are on technology, innovation of the system
worried about their future security and of institution and improvement of the
choose to store their money rather than efficiency of using the production factors.
using it. The first one is that Chines This pattern causes the Chinese
employment rate is not high enough to government to continue to spend a large
ensure that most of people can have a job. amount of money, which forms a vicious
Secondly, in China, the cost of higher circle. In this way, the government’s
education increases. Chinese families expenditure increases causing the
should spend more money each year to percentage of the consumption decreases.
support their children’s education. What’s 5.0 Solutions
more, the pressure of family’s or personal 5.1 Improve the system of
health security increases. These facts in social security
China make it hard for people to spend
their money on consumption rather than The first thing the Chinese
putting it in the banks. Even though government should do is to improve its
Chinese GDP increase with a high speed, social security system in order to ensure
Chinese social security system is still at a citizens’ future security and decrease
low level and can’t catch up with the people’s worry about aftermaths of
growth of Chinese economics. In 2007, consuming. According to the Challenges
the total percentage of the expenditure on and solutions of Chinese consumption-led
education, medicals and social security economy growth, the social security
was only 29.2% of the total expenditure system plays a necessary role in
of Chinese government, which was promoting consumption. A complete
respectively 15.2% and 24.8% lower than social security can motivate citizens to
the countries which have per capita GDP consume rather than storing the money
without worry, increase their ability to citizens start to consume more and
consume and fundamentally increase the more in physical stores or online,
ratio of the consumption in GDP. So what which helps to promote the growth of
can the government do to enhance the the consumption-led economy system.
social security system? First, the However, in countryside and cities
government should continue to extend the which are in second and third classes,
area which the social security system there are not enough physical stores,
covers. Then it should adjust and emend markets, malls or supermarkets. And
its system of levying social security’s fee also shopping online is still not
in order to ensure that the ratio of the popular in those areas. These facts
growth of the levying match the ratio of limit a large number of people’s
the growth of the economics. consumption ability. In this way, it is
5.2 Carry out positive necessary for the government to
employment policies and improve the consuming environment
in those areas where contain a large
ensure citizens’ safety of
consumer group. So first, the
employment government should increase the
Besides improving the system of penetration of the physical stores in
social security, the Chinese government those areas through opener policies
should try their best to improve and and strong supports. Then it should
emend some policies about employment. put greater efforts to publicize the new
Even though Chinese economic grows in shopping way, the online shopping,
a good trend, the employment situation and encourage citizens in those areas
which is the base of citizens’ ability to to use it. Also, the government should
consume is still very severe. In order to carry out some specific policies about
fundamentally enhance people’s will to increasing the safety of shopping
consume, the government should provide online, which provide a new and safer
citizens with a nice employment consuming environment for people.
environment. Here are some ways for the
government to improve the employment
environment. Firstly, Chinese government
should promote and also supervise
enterprises to avoid reducing staffs as
much as possible. Besides, it should
vigorously develop the tertiary industry
and search and set up possible jobs.
What’s more, about the people without
jobs, the government should provide the
best policies, conditions and social
environment for them to start their own
businesses.
5.3 Improve the consuming
environment
What’s more, the government should
enhance Chinese current consuming
environment. These days, urban

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Missouri Academy of Science,

Missouri Academy students sit in the same classrooms side-by-side with

Cultivation of bacterial communities from cave sediments

Figure 1 –a (upper left). Location of the Smallin Civil

Figure 2. Number of colony forming units that grew on

Figure 1-d (lower right). Waterfall at the entrance of the

Table 1. List of closest matches of isolates using NCBI

Figure 3. Gel image of amplicons of the 16S rRNA gene of

Figure 6-a (top). SL59 on a nutrient agar plate; colony is

• Diverse species of bacteria were isolated from the

• Biochemical tests will be run on some isolates for

• We will use next generation sequencing of

• We hope to further characterize these isolates and

• Undergraduate Research Award

• Faculty Senate Grant

Using Characterization Techniques to the Determine the Properties of Porous,

Introduction EDS is used to determine the types of elements found in the

 Understanding the physicochemical properties of

Here, we examine the structure, porosity, chemical

Table 2. shows that a significant amount of the carbon has

Table 3. Summary of index and thickness measurement

Energy Dispersive X-Ray Spectroscopy (EDS)

Figure 3. The porous structure of 3D cubic (left) and 2D

X-Ray Diffraction (XRD) References

3. Ratner, B. D. (1988). Surface Characterization of

University of Missouri College of Engineering

Missouri Academy Research Summer

Life Sciences Summer Undergraduate Research Program

Hunt Research Laboratory

Effect of Temperature and Coverage on Cope’s Gray Tree Frog Capture

• 65 PVC pipes placed at four different ponds in the MOERA area

References and Acknowledgments

The Effect of Biological Nitrogen Fixation in Legumes

Plants use nitrogen to build proteins and it is a crucial

Medicago trancatula: Sinorhizobium meliloti

Lotus japonicus: Mesorhizobium loti

Glycine max: Bradyrhizobium USDA110

3. Measure the length of the plant’s roots and shoots.

4. Stain the roots to observe the bacterial infection

uninoculated plants accumulated anthocyanin due to lack of

Figure 2: Nodule formation and Nitrogen fixation in

contrast, without bacteria plant roots remain non-nodulated

Figure 4: Root-Nodule phenotype of M. trancatula after 2

type and bottom panel shows one of the insertion mutant of

Figure 5: Nodule phenotype of M. trancatula after 2

Figure 6: Growth phenotype of shoot and root, and

Results: Longer shoot and root length, and increased

Abstract Other mutations that cause this disease have also

Fact Sheet : Hemochromatosis. (n.d.). Retrieved

Putting DNA to Work - Inherited Disease -

Immunohistochemical evidence of selective renal sensory denervation after

Abstract reveal the neurotransmitter content of nerves. Neuropeptides

Immunohistochemistry developed a procedure to selectively produce renal afferent sensory

Left Kidneys-RTX treated Right Kidney-Control

Stability Analysis of Metal Oxide Compounds Used in Combustion Reaction

Introduction Gamess is a program that allows performing such

2. Titanium dioxide trichloride (Ti2O2Cl3) – GAFF

3. Titanium dioxide trichloride (Ti2O2Cl3) – UFF

Discussions and Conclusions

Also other metal chloroxide, such as Ti3Cl2O3 and Ti4Cl3O2, or

Effective Diameters of Coated Naproxen Influenced by Concentration of

We cannot make sure that is Kollidon VA64 at 0.3%(W/V)

Additive Manufacturing of AZ31 Magnesium Alloy