2766 J. Phys. Chem.

1994,98, 2766-2781

ARTICLES

Ultrafast Electron Diffraction. 4. Molecular Structures and Coherent Dynamics

J. Charles Williamsont and Ahmed H. Zewail'
Arthur Amos Noyes Laboratory of Chemical Physics,$ Calijornia Institute of Technology,
Pasadena, California 91 125
Received: January 13, 1994'

Ultrafast electron diffraction (UED) is developed, in this and the accompanying paper, as a method for studying
gas-phase molecular structure and dynamics on the picosecond (ps) to femtosecond (fs) time scale. Building
on our earlier reports (henceforth referred to as 1-3), we discuss theoretical and experimental considerations
for the approach. Specifically we show that the use of rotational and vibrational coherences can add a new
dimension to structural determination of gas-phase species. In addition to the internuclear separations of the
molecular sample, the spatial alignment reflected in the scattering pattern contains bond angles and rotational
constants for both excited-state and ground-state species. Vibrational coherence effects are also observable,
and the motion of the wave packet is revealed by the change of the diffraction pattern with time, thus yielding
the molecular dynamics. U E D provides the temporal evolution of the reaction coordinate directly and is well-
suited for studies of global structure changes on this time scale. Paper 5 details our experimental studies with
UED and the current time resolution of the apparatus.

I. Introduction many GED laboratories around the world. The traditional

The interaction between a monoenergetic X-ray beam and the
electronic distribution within a crystalline sample leads to the
formation of a well-defined X-ray scattering pattern. The
scattering pattern is highly sensitive to crystal structure; the
inherent microscopic order of nuclei within the crystal, in terms
of both spatial orientation and position, is projected into the
macroscopic environment by the scattering process. Peter Debye
proposed that structural information about gaseous samples would
also be present in an X-ray diffraction pattern despite the lack
of orientational and spatial order between mo1ecules.l The
structural regularity of individual molecules is still present in a
gaseous sample, and manifests itself in the form of concentric
rings (as opposed to the spotlike patterns from crystals). The
ring pattern is related to a probability distribution of internuclear
distances and reflects the relative locationsof each atom, although
the bond angles and the exact three-dimensional structure are
not immediately evident.
Gas-phase X-ray diffraction was first demonstrated in 1929,
when Debye and co-workers imaged the scattering pattern of
carbon tetrachloride vapor.2 The experiment was more chal-
lenging than crystallographic studies because of the low density
of the gaseous sample, exposure times of several hours, and the
vacuum requirements. Mark and Wierl discussed the feasibility
of using electrons to study gas-phase molecular structure instead
of X-rays. Electrons interact directly with the atomic nuclei
such that electron scattering is several orders of magnitude
stronger than X-ray scattering from molecules. Mark and Wierl
were successful;in 1930 they produced a diffraction pattern from
carbon tetrachloride that was more distinct than similar X-ray
scattering exposures and required a fraction of the exposure time.3
The utility of gas-phase electron diffraction (GED) was
recognized by several investigators,including Linus Pauling here
at Caltech who was interested in using structures to examine the
fundamental nature of the chemical bond. Currently there are
tNational Science Foundation Pre-Doctoral Fellow.
*Contribution No. 8916.
.Abstract published in Aduance ACS Abstracts, February IS, 1994.
0022-3654/94/2098-2766so4.5o/o
experiment begins with a continuous, monoenergetic electron
beam (10-100 keV), typically produced froma hot cathodesource.
The electrons are collimated and directed toward a gaseous stream,
where they scatter and are detected with a photographic plate.
Analysis of the diffraction patterns, however, requires care,
particularly when the molecule has many atoms. The advent of
computer fitting techniques has greatly accelerated the analysis
process.4
The structures of transient intermediates, such as radicals,
was originally studied on the millisecond to microsecond time
scale by flash photolysis combined with spectroscopicprobing.%'
In the past decade, several groups have invoked electron diffraction
as a method for examining these structures. Ischankoet al. created
1-ps electron pulses using an electromagneticchopper and studied
the structure of radical products formed in IR multiphoton
dissociation of CFJ8 (for a recent review see ref 9). Rood and
Milledge conducted diffraction studies on the decompoeition of
ClOz using 100-l.tselectron pulses,1oand recently Bartell and his
group studied the phase changes of clusters on the microsecond
time scale as welLL1 Ewbanb et ai. improved the temporal
resolution of electron diffraction to nanoseconds by combining
a laser-initiatedelectronsourcewitha linear diodeanaydetector,12
and their studies on the laser-decompositionof CS2 are supported
by theoretical calculations. Mourou and Williamson demon-
strated that the diffraction pattern from an aluminum film could
be recorded with a single 100-ps electron pulse and that a phase
transformation of the film could be observed in real time.') With
this resolution, Elsayed-Ali et ai. have successfully shown
reflection high-energy electron diffraction (RHEED) of laser-
heated surfaced4 (Kitriotis and Aoyagi recently reported nano-
second RHEED results's). Solution studies have also been
considered; Bergsma et ai. theoretically predicted the ultrafast
X-ray scattering patterns of solvated iodine; see section IV,part
B.16
Structural changes of isolated molecular systems and reactions
on the femtosecond-picosecond time scale have been probed with
femtosecond transition-state spectroscopy (FTS), where the
experimental time resolution allows observation of the coherent
0 1994 American Chemical Societv
Ultrafast Electron Diffraction
nuclear motion.17 With this in mind, we proposed some time ago
that GED could be used as a variant of the FTS approach to
follow changes in internuclear separations with time for systems
in a molecular The premise is similar to FTZ: a laser
with femtosecond temporal resolution initiates a chemical reaction
within a molecular beam sample, and a second pulse, in this case
an ultrashort electron burst, probes the structural change.18
Two years ago we reported on our first efforts in this direction
with an electron time resolution of -1 ps.19 These electrons
(generated by the photoelectric effect) were accelerated to high
energy (15-17 keV) and directed toward the interaction region,
where the femtosecond pump laser, electron beam, and molecular
beam intersect. The electrons were scattered by molecules in the
interaction region, and the resulting diffraction pattern was
detected with a two-dimensional charge-coupled device (CCD)
operating in direct electron-'-?mbardment mode. The success of
these experiments relied on minimizing the space-charge effects
to maintain picosecond time resolution, and therefore the beam
current was kept very low-up to 8 orders of magnitude below
conventional GED beam currents. Tocompensate, single-electron
detection was invoked.
In conventional FTS experiments the time delay is varied by
delaying the probe pulse relative to the initial t = 0 pulse in a
Michelson interferometer arrangement. A similar design is used
in UED, but the situation is more complicated because the electron
and photon beams have different velocities. This velocity
mismatch was recently shown to be important to the overall time
resolution and must becarefullyaccounted for in theexperimental
design.20 Considerations of temporal and spatial resolutions in
our apparatus are further discussed in the accompanying paper.2'
An important feature of ultrafast electron diffraction is the
formation of a wave packet in the molecular sample, as occurs
with FTS. Both the rotational and vibrational motions of the
molecules are coherent; a degree of order is imposed on the
previously isotropic sample. It is therefore necessary to consider
thestructural changes, both in this regimeof coherent elementary
dynamics and when coherence is subsequently lost. Conversely,
it is possible to exploit the coherent motion to observe new
structural features, as discussed below:
In this article, we turn our attention to the impact of rotational
and vibrational coherences on the scattering pattern in an ultra-
fast electron diffraction experiment. We wish to establish the
nature of the structural and dynamical information that can be
obtained from an experiment which combines high temporal
resolution with high structural resolution. It is shown that an
additional dimension of imaging can be achieved at times when
coherence is induced or recovered-in a sense, Debye's ring pattern
begins to approach the diffraction from a crystalline sample. We
will specificallydiscuss the diffraction patterns which result from
the temporal change of anisotropic distributions and show that
more structural information, including bond angles and rotational
constants, is available than in a conventional experiment. To
predict the impact of vibrational coherence on structural changes,
we present studies of the time-dependent scattering patterns for
both dissociative and bound-state systems with the help of
molecular dynamics simulations. We illustrate our points by
first considering the structural changes in diatomics and then
examining more complex molecular systems of, for example, five
or eight atoms.
The paper begins by highligh ting relevant aspects of gas-phase
electron diffraction theory. This brief outline provides a basis
for much of the theoretical analysis presented later, when we
consider the effect of coherence on the diffraction pattern.
Rotational coherence is discussed in section 111, and we show
"snapshots" of the diffraction patterns that result from different
combinations of polarization and excitation. We also examine
the impact of rotational coherence on the analysis of dissodiation
products and molecules with more structural complexity than a
diatomic. The effects of vibrational coherence are considered in
section IV. Our conclusions are presented in section V.
The Journal of Physical Chemistry, Vol. 98, No. I I, 1994 2767
II. Time-Independent CED Theory
The general theory of gas-phase electron diffraction has been
described elsewhere (see, for example, refs 4, 22, and 23). This
section presents a theoretical framework with which to consider
the effects of rotational and vibrational coherence. The incident
electron beam is defined by wave vector b,where the magnitude
of is related to the de Broglie electron wavelength by lbl =
2a/X. The incident electron beam is perturbed by the electronic
potentials of the molecular sample and subsequently scatters with
wave vector k at an angle 0. If the scattering process is elastic
lkl), then the momentum transfer vector s may be written
sZ16-k (1)
The magnitude of the momentum transfer is
4a
Is1 = 21161 sin(6/2) = sin(8/2) (2)
The total scattering intensity, I, is the sum of contributions
from atomic (I*) and molecular scattering (fM). These intensities
vary with scattering angle and are usually expressed as a function
of s rather than B
If it is assumed that the electronic potentials of each atom in the
molecule are independent (the independent atom model), then
the atomic scattering intensity may be written as a sum of elastic
and inelastic scattering contributions
In this equation, N i s the number of atoms in the molecule,fi and
SIare the direct elastic and inelastic scattering amplitudes for
atom i, a0 is the Bohr radius, and Cis a proportionality constant.
The contributions from spin-flip scattering amplitudes (gi)have
not been included as they are generally neglected for high-energy
electron diffraction experiments24
The molecular scattering intensity is composed of interference
terms which contain structural information about the scattering
center. The intensity is written as a sum over all internuclear
separations:
N N
7#I
where qris the complex phase term for the corresponding scattering
amplitude fr, and rij is the position vector between atom i and
atomj. The interaction between incident electron and scattering
molecule is extremely f a s t - o n the order of attoseconds-and
the molecular scattering intensity must be averaged over all
populated vibrational and rotational states in the molecule.
Vibrational averaging contributes an additional exponential term
(the Debye-Waller factor) that is dependent upon I , the mean
amplitude of vibration
This factor represents the replacement of a specific internuclear
separation with a weighted distribution corresponding to the
vibrational motion between the two atoms.
If the molecules have not been prepared in a specific rotational
state, then the rotational average is equivalent to an average over
2168 The Journal of Physical Chemistry, Vol. 98, No. 11, 199'4
all spatial orientations at the inst--it of scattering. The molecular
scattering intensity for a spatially isotropic sample takes the form
wherejo is the zero order spherical Bessel function, or sin(sr,)/
srij-
The scattering amplitudes,ft andfi, decrease with the square
of s (ref 25), so the total scattering intensity decays like d;as
a result, a graph of the modified molecular scattering intensity,
sM(s),is better suited for revealing the fine details of the scattering
signal than a plot of the total intensity
where a and b correspond to two atoms in the molecule. As
mentioned above, the molecular scattering function contains all
of the structural informationabout the molecule, but an illustrative
interpretation of experimental results is provided by taking the
sine transformof sM(s) andexaminingflr), the radial distribution
function
f i r ) = JomsM(s)sin(sr) ds (9)
The radial distribution function plots the relative density of
internucleardistancesin the molecule. This transform relationship
is strictly true only in the case of pure elastic scattering from a
homonuclear diatomic molecule,23but f(r) is nevertheless very
useful for a qualitative understanding of the structure of more
complicated systems. The range of experimental scattering
intensity is limited by some maximum value smax (e.g., 10-15 A-1
for the UED experiments reported in the accompanying paper),
and the experimental radial distributionfunction typically includes
an exponentialdamping term to filter out artificial high frequency
oscillations
f(r) = JosmusM(s)exp(-k,.,s2) sin(sr) d s
(10)
It should be noted that all data analysis and fitting procedures
are performed on the experimental molecular scattering function,
and not the radial distribution.
The scattering factors which appear in the above equations cf,
7,S ) are functions of the atomic number 2 of the scattering
atom, the energy of the incident electron beam, and s. These
factors may be obtained from published tables.25 All scattering
intensities and molecular dynamics calculations reported here
were computed with the C programming language on an IBM
PC compatible. The incident electron energy was assumed to be
40 keV, ,s was limited to 15 A-1, and the radial distribution
function damping constant (kd)was set to 0.01 A2.
111. Coherent Spatial Orientation
In UED experiments, the molecular spatial-orientation dis-
tribution is dependent on the polarization of the laser and the
type of transition accessed. If Q is the angle between the molecular
transition moment and the polarization of a linearly-polarized
laser pulse, then immediately after a parallel dipole transition
the number of excited molecules at angle Q is proportional to cos2
Q. If the excitation probability is unity, then one-third of the
sample is pumped into a higher state and the remaining unexcited
molecules must have a sin2 Q distribution. In effect, the pump
laser converts the isotropic sample into an anisotropic mixture of
excited and unexcited molecules with well-defined spatial ori-
entation distributions. The duration of the anisotropy, however,
lasts only until rotational motion randomizes the spatial orientation
Williamson and Zewail
again: after several picoseconds the sample will again be isotropic,
albeit a mixture of excited and unexcited molecules.
Rotational motion is quantized and the rotational frequencies
are commensurable (or nearly so), and barring any collisions,
there will be some later time in which all the molecules return
to their original spatial orientation. The short-lived anisotropic
distribution will therefore appear again and again aver the course
of many nanoseconds.26 This phenomenon, known as rotational
recurrence, has been extensively studied in the context of time-
resolved spectroscopy experiments, where rotational recurrences
have proven useful for determining structures of large molec~les?~
The period of the recurrence in a symmetric top molecule is equal
to 1/ ( 2 8 ) where 8,the rotational constant, is related to the speed
of light c, Planck's constant h, and the moment of inertia 16 by
B = h/8r2Zbc. For asymmetric tops, the key observables are A,
B, and C.
It has been shown that the temporal width At of the recurrence
is related to the temperature T and the rotational constant by27
where B has units of cm-l and T i s in Kelvin. For example, the
first recurrence of tram-stilbene (B = 0.252 GHz), occurring
1.95 ns after excitation, has a full width at half maximum (fwhm)
of 21.Ops at 5 K and 6.8 ps at 50 K, and these calculations26have
been experimentally tested. In a diffraction study of rotational
recurrences, only spectroscopic information about the initial
excitation transition is required; the recurrences would be probed
by following the diffraction pattern in time, as opposed to further
excitation to another state with a second ultrafast laser pulse.
Kohl and Shipsey showed theoretically that the diffraction
pattern from molecules in a specific rotational state, with a well-
defined nutation axis, is not cylindrically symmetric and contains
extra clues about themolecular structure.28 The molecular sample
in UED, however, gains a different type of rotational order.
Rotational states are coherently populated by the excitation laser,
but the judicious combination of a dipole transition, quantized
rotations, and high temporal resolution creates an ordered spatial
orientation distribution. We might expect that the diffraction
pattern of a spatially anisotropic sample will contain more
structural information than a conventional GED pattern. Equa-
tion 5 must therefore be reexamined to ascertain what the impact
of an anisotropic spatial orientation distribution formed by
ultrafast laser excitation will be on diffracting electrons. These
effects must be considered at short times, immediately after
excitation, and over longer times, when the recurrences take place
and the anisotropic distribution reappears. To emphasize the
changes in the diffraction patterns, it will be assumed that the
excitation probability is unity. Experimentally, however, the
probability will be one-half at best because of stimulated emission
and saturation effects, unless the upper state is dissociative or
Rabi cycling is introduced.
Fink et af., treated the alignment problem for molecules
spatially oriented in a hexapole field.29 They have suggested that
changes in electron scattering would be potentially useful for
diagnosing the degree of spatial alignment in molecular beams,
and their most recent experimental work has shown agreement
with the theoretical predictions.30 The geometrical framework
presented by Fink et af. describes their alignment studies well,
but more degrees of freedom are necessary for modeling the
experimental arrangement discussed here. We outline our
methodology in part A of this section. Part B follows with a brief
synposis of the diffraction patterns generated by molecules in
total spatial alignment; this synposis will assist in interpreting
the more complicated patterns from laser-excited samples. The
theoretical diffraction equations for the molecular subset selected
by linearly-polarized lasers in parallel and perpendicular con-
figurations are established in parts C and D, and we will discuss
their application to UED rotational recurrence studies of
molecular iodine in part E. Part F concludes this section by
Ultrafast Electron Diffraction
Scattering
Center
Figure 1. Electron scatteringgeometrydefined in the text. The incident
electron beam travels toward the scattering center along the z-axiswith
wavevector h.The position vector between atoms i and j , ru. is defined
byaltitudeanglen(relativeto ther-axis) andazimuthalangle+((relative
to thex-axis). Electronsscatter at angle0 with wavevector k and intersect
theplaneofthedetectorat angle$ (relativetothex-axis). Themomentum
transfer vector is s. In a UED experiment, the excitation laser travels
toward the scattering Center along the y-axis.
- = srij[sin(8/2) cos Q - cos(8/2) sin Q cos(@- $)I
Y
"8
b, 8s:
0G."3 ec-
-#la
Molecular Sample
(Isotropic)
Detector
FigureL Electronscatteringfromanisotropcsampleofmoleculariodine.
On theieftisaschematicoftheinterscnionbetween theincidentelectrons
and the molecular sample. On the right is a perspective view of the
resulting modified molecular scattering pattern, sM(s). The scattering
pattern consists of cylindrical oscillations with frequency r1.112~.
evaluating the structural information present in the anisotropic
diffraction pattern from a more complicated molecule, trifluor-
nmethvl inrlid~.
A. Theoretical Framework. The scattering intensity, I,, of
a laser-excited molecular sample must be extracted from eq 5 ,
and to simplify this derivation we will initially consider only the
scattering from position vectors rij which are parallel to the
molecular dipole transition axis. This is sufficient for describing
all diatomics and linear molecules; more complicated molecules
with nonparallel position vectors will be considered in part F.
The vibrational period of most chemical bonds is significantly
faster than a few picoseconds, and thus the starting point for this
analysis is actually eq 6, where the vibrational motion has been
separated from the average. In the context of UED, the average
over rotational states should be evaluated as an average over
spatial orientation since many rotational states are populated;
the important perturbation is the initial (and subsequent recur-
rence) spatialorientationdistributionselected with theexcitation
laser polarization. Equation 6 may he rewritten as:
Ids) = cccKjKl
N N
i=1 j=1.
exp(- ~i~sz)Re[ei'"'"JFij(s)l (I2)
I*J
where
The Journal of Physical Chemistry, Vol. 98, No. I I . 1994 1769
Fij(s) = (eiar'9Spa,ial (13)
Fjjcontains the spatial average of the scattering function for a
specificinternuclear separation. Note thatFjjisa functionofthe
momentum transfer vector s, and not just its magnitude.
Figure 1 presents the geometrical frame of reference we have
chosen to evaluate Fjp The incident electron beam travels along
the z-axis, and the position vector rjj is oriented relative to the
z- and x-axes by an altitude angle Q and an azimuthal angle $,
respectively. Diffracted electrons strike the two-dimensional
detector at a position determined by the scattering angle 8 and
the rotational angle @ (defined relative to the x-axis)." In this
coordinate system, the momentum transfer vector is written:
s = k,(-cos @ sin 8, -sin @ sin 8, 1 -cos 8)
= s(-cos $ cos(8/2), *in @ cos(8/2), sin(8/2)) (14)
and the position vector is written
rij = rij(sin Q cos $, sin Q sin $, cos 0 ) (15)
The dot product of these two vectors simplifies to
siij (16)
Todetermine Fil,thescattering function ei'"umnst beintegrated
over thesurfaceof thespheredefined by nand$. Theanisotropic
spatial orientation is included by multiplying the scattering
function with an appropriatedistribntion function,P(Q,$), before
integration
Mathematicaldetailson theevaluationofthis integral for several
relevant distribution functions have been consigned to the
Appendix. For the case of an isotropic distribution (P(Q,$) =
I), the results is:
asexpected. andthccorresponding two-dimensional plot ofsM(s)
for molecular iodinc is presented in Figure 2 uith a drawing of
the molecular sample. The frequency of the oscillations in this
familiar ring pattern is equal to q.t/2x. wherc rl.l = 2.666A.I2
B. Diffraction from Total Alignment. With the theoretical
framework defined in part A, electron diffraction patterns from
a laser-prcparcd molccularsamplc may be predicted. It is useful.
howevcr,tofirstconsider thescattering pattern froma molecular
sample with tntal spatial alignment. The functional forms of
there pattcrnr require no integration and may bederivcd dircctl)
from cqs 6and 16. Twodifferent fundamental arrangcmcntsare
possible: (1 J all molecules arc oriented parallel to the direction
of the incident electron beam, and ( 2 ) all molecules are oriented
perpendicular to the direction of the electron beam.
In the firrt case (0= 0, thc bond axis is parallel to the z-axis).
the Scattering function for iodinc is equal lo
The diffraction pattern is cylindrically symmetric and its
section is an oscillatory function that changes slowly with s at
small scattering angles (ka >> s). As shown in Figure 3, the
modified molecular scattering pattern is an order of magnitude
more intense than electron scattering from an isotropic distri-
bution, but the slow onset of the oscillations makes it difficult to
extract structural information. This has a physical interpre-
tation-the molecules are struck by the electrons end on, and the
second atom is "hidden" by the first atom along ko. Although
2770 The Journal ofphysical Chemistry. Vol. 98, No. 11, 1994
s (A-I)
Figure 3. Modified molecular scattering cross sections from diatomic
iodine in three different spatial distributions: (1) isotropic, (2) total
alignment parallel to the incident electron beam (z-axis), and (3) total
alignment perpendicular to the incident electron beam and parallel to the
x-axis. The scattering intensity from the isotropic sample is an order of
magnitude lessthan thescattering intensity from spatially alignedsamples.
The oscillation frequency of interference fringes from the parallel
configuration is very slow for small s; the first cycle finishes at s = 22.2
A-'. Scatteringfrom the perpendicular configurationis not cylindrically
symmetric. The interference fringes along the x-axis (parallel to the
internuclearaxis) arestrong,and the frequency issimilar tothe frequency
oftheisotropicfringes. Therearenooscillationsalong they-axis (normal
to the internuclear axis).
the number of cycles increases with the square of s, there is little
information present in the range of s available to UED.
In the second case, when all molecules are spatially oriented
perpendicular to the electron beam (R = 712, J. = 0, the bond
axis is parallel to the x-axis), the scattering function is
Theprescnccofthccosotermdestroys thecylindricdlsymmetry.
Thcreare nooscillationsa1ongthe)-axis, whereo = f ~2 (Figure /
3). while the oscillations which exist along the x-axis have a
period similar LO the intcrlercncc fringes from an isotropic
distribution and are an order of magnitude larger.
A tuo-dimensional plot of s M ( s ) for this second case. shown
in Figure 4. clarifies the connection hctwecn the horizontal and
vertical cross sections presented in Figure 3. The diffraction
pattcrn from spatially-oriented molecules parallcl to the x-axis
is a series of linear fringes, as opposed to cunccntric rings. This
figure is similar tothe interference pattcrn from Young's doublc.
slit light bcattcrine- exocriment;
. in fact. the scattered electron
intensity of eq 20 may he wriken in a'form analogous to the
diffractedlight intensity froma pairofslitsseparated hya distance
d3'
(for 6 = 0) (21)
The potential wells of the two iodine atoms effectively function
as a pair of "slits" for the incoming electrons, and the pattern
Williamson and Zewail
* 8'
88%
9
Si8
Molecular Sample
(Perpendicular) ..
Iletector
Figure 4. Electron scattering from a sample of molecular iodine with
total spatial alignment. The bond axis ofeach molecule is parallel to the
x-axis. On the left is a schematic of the intersection betwecn the incident
electrons and the molecular sample. On the right is a perspective view
afthecorrespandingmodifiedmolec"larscattering,sM(s).Theamplitude
ofthe interference fringes is approximately an order of magnitude larger
than the interferencefringes from the isotropic sample (see Figures 2 and
3).
shown in Figure4resultsfrom interference between theelectrons
diffracted by these two scattering centers.
Total alignment of the iodine molecules has affected both the
amplitude and the frequency of the interference fringes in the
diffraction pattern. The amplitude has increased by an order of
magnitude, which implies that the signal-to-noise ratio for
molecular scattering from spatially-oriented molecules is larger
than isotropic scattering. We might expected that this increase
in signal-to-noise will counterbalance the decrease in the per-
centage of molecules contributing to the anisotropic diffraction
pattern in an actual experiment.
The oscillation frequency of the diffraction signal from the
first case (the parallel configuration) is significantly different
from the s a n d case (the perpendicular configuration). Struc-
tural information is more difficult to obtain from a parallel
configuration because the first few oscillations are very slow, and
the diffraction pattern would have to be measured out to large
values of s. The oscillation frequency of the fringes in the
perpendicular configuration, rt.I( 1 - (s/Zk0)911'/27, approaches
the frequency of the isotropic distribution,r1_1/2~,athigh electron
energies where ko is large. As will be emphasized in part F, the
perpendicular configuration also contains information about bond
angles. Thediffraction pattern in Figure4 tells theexperimentalist
that the iodine bond axis is parallel to the x-axis; if J. is nonzero,
then the interference fringes would be similarly rotated on the
detector hyangleJ.relative to thex-axis. Thediffraction pattern
from more complicated molecules is a sum of contributions from
individual atom pairs, and interference fringes in the diffraction
pattern will reflect the differing spatial directions of the various
rjj.
C. Parallel Excitation. The laser beam, electron beam, and
molecular beam are all mutually orthogonal in our UED
e~periment.~ This
~ , ~experimental
~ design is motivated by ease
of construction and a desire to reduce velocity mismatch
broadening in the total temporal resolution of the experiment.z0
We will now consider the diffraction patterns which result from
molecules excited by a linearly polarized laser traveling toward
the scattering center along the y-axis, such that the polarization
vector is parallel to the wave vector b. For now it is assumed
that scattering takes place before the molecules have time to
rotate out of their initial distribution and that the entire subset
of molecules is excited. The scattering pattern at later times will
be considered in part E.
The spatial orientation distributions of both excited and
unexcited molecules will be cylindrically symmetric about b,
and the diffraction pattern should reflect this symmetry. For a
Ultrafast Electron Diffraction
I ~ I*otroPic Excited ---- Unexcited 1 X l
Figure 5. Modified molecular scattering c r w scctioni of ground-rmtc
i d i n c from spatial urientation di,tribuuonscrcated by a linrirly pulanied
laser. The polariration vector is parillel to ko and the molcculu dipole
trmsitiun i s a w m e d to be parallcl.sothc I~WCIEIIC muleculcsurwntcd
porollpl to the electron beam Thc intcnrit) of the in1crfcren:c fringes
from thi,subsct ofthc molecular sample isan ,irdcruimagnitLdr.rmaller
than the interfcrcncc fringcs from the isotropic simple. The 0,cillition
f r c q x n c y is similar. but r 2 ridianr out ut phdrc. 'The intcrfcrencc
fringes from the unexcited sub,et are m x l a r i n inlcnsit) and frcqucnc'!
to the isotropic m t i r r m g pattern
parallel dipole tranbition. theorientation of the intcrnuclcar axis
ofthecxcitcd molecules will haveaspatialdisrributionofP(R.J)
=cosZR Thcspaual di5tribution ofthe unexcited molcculcsuill
therefore be P(R.$)=sinzl.l. Turciter~te,ueareonlyconsidering
position vectors which 3rc parallel to the cxsitation axis, and the
excitation probability IS unity. Integration of eq 17 using these
distribution5 yields the following functions for F,, (see Appendix)
parallel, excited
parallel/unexcited
j, b v 1
Fii(s) = jo[sr..] -~srii
'J
+ sin2(O/2)j2[srii] (24)
As expected, these functions are independent of 4. The modified
molecular scattering function ofthese two distributions for ground-
state iodine are plotted with the isotropic distribution in Figure
5 . The scattering contribution from the parallel/excited subset
of molecules is relatively weak; evidently the strong scattering
signal observed in part B (when all molecules are oriented parallel
to the electron beam) is rapidly washed out by interference with
scattering from molecules slightly off-axis to the electron beam.
Because this contribution is weak, the oscillation frequency of
thescattering intensity from the parallelJunexcited subset isnearly
identical to the isotropic distribution. The oscillation frequency
from the parallel/excited subset is similar, but phase-shifted by
~ 7 1 2 Sincealldistributionsarecalculatedfor
. thesamespecies,
the sum of the two scattering signals is equal to the diffraction
signal from the isotropic distribution. Consequently, if the excited
species is structurally identical to the unexcited species, the
diffraction pattern will not change.
Structural information inthe diffraction pattern from a sample
with total parallel alignment was identical to the information
from an isotropic distribution but more difficult to extract, and
thesameis trueforthediffractionsignal from theexcitedJparallel
subset. Like the isotropic pattern, the excitedJparalle1 signal
depends only on the magnitudes of the position vectors. It would
bedifficult, however, todetermine the molecular structureof the
excited-state species because the low amplitude signal is masked
by the diffraction signal from the unexcited molecules.
The Journal of Physical Chemisrry. Val. 98, No. 11, 1994 2111
L 2 -10 s,
Y
Molecular Sample
(Perpendicular 1 Excited) .-
Detector
Figure6. Electron scattering from thesubsetofa ground-statemolecular
iodine sample excited by a linearly polarized laser. The polarization
vector is parallel to the x-axis and the molecular dipole transition is
assumed to be parallel. On the left is a schematic of the intersection
between the incident electrons and the perpendicular/ercited subset of
the molecular sample. On the right is a perspective view of the
corresponding modified molecular scattering, sM(s). The scattering
pattern resembles a cross between diffraction from an isotropic sample
(Figure 2) and a totally aligned sample (Figure 4). The interference
fringes along the x-axis are similar in intensity and amplitude to the
interferencefringes from an isotropic sample. The interference fringes
along the y-axis are weak and resemble the scattering pattern from the
parallel/excited subset shown in Figure 5 .
D. Perpendicular Excitation. Significantly different effects
are observed when the polarization vector of the laser is parallel
to the x-axis and perpendicular to ko. As in the example of total
perpendicular alignment, the scattering pattern loses its cylindrical
symmetry because the spatial orientation distribution selected
with the polarized laser is not symmetric about the z-axis. With
an excitation probability of unity, the distribution of the excited
moleculesisdefinedby P(Q,$)=sin2acosz$andthedistribution
of the unexcited molecules is (1 - sin2 a cos2 $). Integration of
eq 17 with these distributions is discussed in the Appendix and
leads to the following functional forms for Fij:
perpendicularJexcited
+
Fij(S) = j'[sriil cos2(S/2)j2[srii] cos26
~
(25)
sr..'I
perpendicularJunexcited
As in the parallel case, the sum of these two functions is jo[sr,].
the iso:ropic scattering distribution, but note that the presence
of the cos2 6 term means that each function is not cylindrically
symmetric. A two-dimensional plot of sM(s) for the perpen-
dicular/excited subset of molecules is shown in Figures 6 and 7a,
and theperpendicular/unexcitedcaseisshowninFigure7b.These
are calculated for ground-state iodine, Both patterns appear to
be a cross between isotropic scattering (Figure 2) and scattering
from a sample with total perpendicular alignment (Figure 4),
and despite the fact that only one-third of the molecules are in
the perpendicular/excited subset, the amplitudeof the interference
fringes along the x-axis is as strong as the isotropic distribution.
Furthermore, the 4 dependence of the fringes indicates the
directionality of r,., as was discussed in part B.
The two-dimensional radial distribution functions of the
isotropic distribution and the perpendicular/excited distribution
are shown in Figure 7c,d. Admittedly, taking the sine transform
of the function in eq 25 to extract the radial distribution is a
crude approximation, and this is reflected in the fluctuating
baseline of the surface (Figure 7d). We will consider more
2172 The Journal ofphysical Chemistry, Vol. 98, No. 11, 1994 Williamson and Zewail

Internuclear Separation (A) Internuclear Separation (A)

Figure 1. Diffraction from ground-state iodine. (a) sM(s) for the perpendicular/excited subset, This pattern was also shown in Figure 6. (b) sM(s)
for theperpendicular/unexcited subset. Theunexcited molecules are aligned parallel to the excitation laser (along they-axis), sotheinterference fringes
are strong along the y-axis and weak along the x-axis. (c) Two-dimensional radial distribution curye from an isotropic sample of ground-state iodine.
The ring is located at -2.1 A. Only one quadrant is shown. (d) Two-dimensional radial distribution curve from the perpendicular/excited subset
of the molecular sample. The intensity at 2.1 A is strong along the x-axis and weak along they-axis. This reflects the physical orientation of the iodine
sample in the labratory frame of reference. Only one quadrant is shown.

appropriate techniques for extractingf(r) in future publications.
For now, however, the sine transform is sufficient to provide
excellent qualitative information, and when scattering from
trifluoromethyl iodide is considered in part F, the radial
distribution function will provide a description of the structure
that is easier to interpret by visual inspection than the molecular
scattering function. As might be expected from the appearance
of the perpendicular/excited molecular scattering function, the
corresponding radial distribution function also indicates the
directionality of the iodine-iodine internuclear separation during
the experiment. The disappearance of the 2.7-A peak along the
y-axis reflects the fact that most molecules oriented parallel to
the laser beam axis are not in the perpendicular/excited subset
aftera parallel dipole transition. The radial distribution function
corresponding to the perpendicularlunexcitedsubset(not shown)
contains a peak along the y-axis and no peak along the x-axis.
E. Experimental Applications: Ground- and Excited-State
Structures. Thediffraction pattern from laser-prepared molecules
differs from the isotropic pattern because excitation is a selective
process that depends on the spatial orientation of the molecular
dipole. Thisdifferencewillnot beseen, however, ifthemolecular
structuresofthe twostatesaresimilar becausethetotaldiffraction
pattern is always a sum of scattering from the excited and the
unexcited subsets; if the two species have identical r,, then this
sum is just jo[srjj]. Fortunately, the excited-state structure is
usually changed from the ground-state species to some degree,
and electron diffraction is quite sensitive to small changes in
molecular structure. For example, Figure 8 shows that there is
a clear difference between the radial distribution curves corres-
ponding to the lowest vibrational levels of ground-state iodine
andof B-stateiodine. In thenext few paragraphs, we willconsider
how to combine rotational coherence effects with the diffraction
patterns discussed in parts C and D such that more structural
information about thescattering molecules can be extracted than
in a conventional gas-phase electron diffraction experiment.
With an isotropic distribution, it is possible to improve the
signal-to-noise ratio by summing the total scattering intensity a t
a constantvalueofson thedetector. When the laser polarization
is parallel to the electron beam, the diffraction patterns from
excited and unexcited subsets are cylindrically symmetric and
may therefore beaveraged ina similar way over theentiredetector.
We haveseen, however, thatthisarrangementonly leads tosubtle
changes in the diffraction pattern, and that these patterns do not
appear to contain any extra structural information. We will
instead turn our full attention to excitation with the laser
polarization perpendicular to ko.
In this case, the diffraction pattern loses cylindrical symmetry
and the signal cannot be averaged over the entire detector.
Variations in thediffraction pattern must be particularlydistinct,
and ideally there would be some way to separate the scattering
signal of the excited species from the unexcited species. The
scattering patternat early times,in theinstant after themolecular
 -b
Ultrafast Electron Diffraction
Ground
Exclled State
s state. The ground state molecules are also assumed to be in the
0 1 2 3 4 5
Internuclear Separation (A)
Figure 8. Radial distribution curves for ground-state (X) and excited-
state (B) iodine at vibrational level Y = 0.
0 early-time amplitudealong thex-axis,assuming that the excitation
5 10
5 10
0 10
5 species are different, and the recurrences will be separate and
5 10
Figure9. Modified molccularscatteringcuwesfromamiitureofground-
state and B-state iodine. (a) Scattering pattern immediately after
excitation. The excited iodine is in a perpendicular/excited distribution
and the ground-stateiodine 1s in a perpendicular/unexciteddistribution.
The oscillation frequency along the x-axis is slightly greater than along
they-axis, which reflects that B-state molecules (q.1 = 3.027 A) in the
sample are oriented parallel to the x-axis and the unexcited molecules
@ . I = 2.666A) areoriented parallel to thcy-anis. (b) Scattering pattern
a few picoseconds after excitation. The spatial anisotropy has been lost
due to rotational motion. The diffraction pattern now corresponds to an
isotropic sample of'/, ground-state icdine and I / , B-state icdine.
sample has been excited by the polarized laser, should be
considered first. The excited and unexcited molecules have not
hada chanceto rotateout oftheiranisotropicspatial distributions,
The Journal of Physical Chemistry, Val. 98, No. 11. 1994 2113
although they will have undergone several vibrations. Perhaps
the simplest experiment of this type is excitation of iodine from
the X state to the bound B state (a parallel dipole transition). For
demonstration purposes, the influenceof Franck-Condon overlap
will be ignored, and it is assumed that the excitation laser places
ground-state molecules into the lowest vibrational level of the B
-
lowest vibrational level. (A more detailed investigation of the B
X transition must account for the impact of overlap and
vibrational motion and is delayed until section IV.) The resulting
diffraction pattern is a sum of the perpendicular/excited dis-
tribution (eq 25) evaluated for the B state (11.1 = 3.0267 A, 11.1
= 0.04598 A) plus the perpendicular/unexcited distribution (eq
26) evaluated for the X state (11-1 = 2.6664 A, 11.1 = 0.03519
.&).I4 The modified molecular scattering pattern from this system
(Figure 9a) reflects the anisotropy of the sample. It is clear that
the oscillation frequencies along the x- and y-axes are different,
but extracting informationon the excited-statespecies is nontrivial
because the background signal from the unexcited molecules also
depends on 4. Other possible approaches should be considered,
as discussed below.
Iodinemay beexcited toadissociativestate insteadofa bound
state. The dissociation time is very fast-within a few hundred
femtoseconds"-so shortly after excitation the molecular sample
will consist of atomic iodine in the perpendicular/excited
distribution and molecular iodine in the perpendicular/unexcited
distribution. The diffraction pattern will therefore he equivalent
to Figure 7b. The change in the diffraction pattern is certainly
distinct, and additional structural information about the ground
state species has been determined-the directionality of rl.l.
Over longer times, the anisotropicdistribution ofthe unexcited
iodine molecules will be lost due to rotational motion, and the
electron diffraction pattern will correspond to an isotropic
distribution. The amplitude oftherings will be two-thirdsofthe
laser has dissociated all of the molecules in the perpendicular/
excited subset. Approximately 1 / 2 8 picoseconds after laser
excitation, however, a rotational recurrence will take place and
the anisotropic distribution will appear once again. (A half-
recurrence will also occur earlier at 1/48 P S . ) ~By ~ taking a
series of diffraction patterns in time, it will be possible to mimic
the spectroscopic rotational recurrence experiments of Felker et
ai. and determine the rotational constant with UED. The
experimentalist looks for those times at which the isotropic
distribution changes to the anisotropic pattern. Rotational
recurrencestudiesoftheground-state species are therefore possible
with UED.
Observing rotational recurrences with UED is a time-domain
technique for measuringrotational constants, but these rotational
recurrences are useful for distinguishing bctween the structures
-
of ground-state and excited-state species. Recall that the early-
time diffraction pattern from excitation of the B X transition
was anisotropic hut did not distinguish well between the excited-
and ground-state species. This will not be the case at later times
because the rotational constants of the ground- and excited-state
distinct. As an example, with ground-state iodine (v = 0). EX =
0.0373 cm-I and 1/2& = 447 ps; for iodine in the B state ( v =
0), BE = 0.0289 cm-' and 1/2& = 577 ps." These recurrences
are well-resolved in time, and the scattering pattern at each
recurrence will correspond to a sum of one species in an isotropic
distribution and the second species in its initial anisotropic
distribution. Studies of the excited-state species are best
conductedwithanunpolarizedlaser,~~ thatthediffractionsignal
for the excited species is a sum of the parallel and perpendicular
distributions. Although the parallel contribution does not add
much to the scattering pattern, the isotropic background signal
from the unexcited molecules is reduced by a factor of 2. The
excited pattern is easier to discern because only onc-third of the
sample remains unexcited.
1114 The Journal of Physical Chemistry. Vol. 98, No. 1 1 , 1994
0 10
5 correct this, we willexamine thescattering pattern fromall position
s, 10
0 primed m r d i n a t e system may he transformed to the unprimed
5 . ' 10
s, 10
Figure 10. Modifiedmolecularscatteringcurvesfromamixtureofground-
state and B-state iodine during subsequent rotational recurrences. (a)
447 ps, ground-state rotational recurrence. The molecular sample has
been excited witha linearly polarized laser polarization parallell ox-axis)
and is ' 1 3 B state, 2/3 ground state. Ground-state iodine returns to a
perpendicular/unexcited spatial distribution. B-state iodine remains
isotropic. (b) 577 ps. B-staterotationalrecurrence. The molecularsample
has been excited with an unpolarized laser and is therefore B state,
' 1 3 ground state. B-state iodinereturns to an unpolarized/excitedspatial
distribution. Ground-state iodine remains isotropic.
The scattering patterns for molecular iodine a t 447 and 577
psarepresented in Figure IO. At 447 ps, theinterference fringes
corresponding to ground-siaie iodine are enhanced along the
y-axis; similarly, a t 517 ps the interference fringes of exciied-
Sioie iodine are enhanced along the x-axis. In both figures, the
x- and y-axis scattering profiles are different in frequency and
amplitude; separation of the ground- and excited-state scattering
patterns has been accomplished by exploiting the differences in
the period of the rotational recurrences in UED. Note that the
temporal and spatial characteristics of this experiment enhance
the capability of electron diffraction to give both ground-state
and excited-state structures.
F. More Complicated Molecules, CF& The enhancement of
the interference fringes shown in Figure 10 is perhaps a little
misleading because iodine is a simple diatomic molecule. In
general, the scattering pattern of a molecule with many atoms
is a sum of different frequency components from the various
internuclear separations, and therefore the total signal results
from a combination of constructive and destructive interference
between these different components. Furthermore, the scattering
theory developed in part A does not adequately describe more
complicated molecules because we only considered position vectors
Williamson and Zewail
Figure 11. (a) Structure of trifluoromethyl iodide. (b) Spatial distri-
butions of the four CFlI pition vectors after a parallel molecular dipole
IransitionalongtheC-Ibondaris has beenexcited. The threcremaining
position vectors (TCF. rF.+. rF-1) sweep out cones definedby an angle Rtj.
where Rjj is the angle between IGI and rp
which were parallel to the molecular dipole transition axis. To
vectors in CFJ after the moleculehas been excited along a dipole
transition parallel to the C-I bond.
The structure of CFJ is shown in Figure 1la. Excitation of
a dipole transition parallel to the C-I bond is insensitive to the
angular position of the fluorine atoms around the C-I axis, and
thescatteringpattern must amount for an averageoverall possible
rotational orientations of the other internuclear separations. As
demonstrated in Figure 1Ih, each position vector r, sweeps out
a cone about the C-I axis; the angle between the C-I axis and
each cone is defined by RIP The geometry of this arrangement
is shown in Figure 12. The angle a defines the angular position
of rv about the excitation axis, and in the primed coordinate
system, rlj is
rij = rij(sin Rij cos a,sin Rlj sin a,0) (27)
where Olj is the angle between rij and the excitation axis. The
coordinate system according to
sin R cos $
El [
= rlj cos Ro sin R sin $
cos0 1 +
cos !
[
l $ -sin $ sin R cos J.
cos
cos R sin $ cos $ sin R sin $
+in O 0 cos
Application of this transform to eq 27 leads to
][I:] (28)
r.. =
(sin R4 cos a ws D + cos Do sin D) cos *-sin Oil sin a sin J.
[ +
rlj (sin O,j COS a cos R ws R, sin R) sin *-sin D,j sin a cos J.
cos R4 cos R - sin R, cos 01 sin J.
(2%
1
Note that if rlj is parallel to the excitation axis (O,j = 0)then eq
29simplifiestotheearlierdefinitionofr4(eq15). Themomentum
transfer vector, s, is not dependent on R, and a,but Fij must now
include a third integration about the circle defined by a and r,
sin 0,
It is important to note that the weighting distribution P is
independent of Rlj because P depends only on the angle between
the excitation axis (the C-I bond in the example discussed here)
and the laser polarization axis. The inner integral may be
evaluated analytically using an identity discussed in the Appendix.
The resulting double integral was integrated numerically using
Ultrafast Electron Diffraction
Mathematica and analysis of these molecular scattering curves
led to the following equation for the perpendicular/excited
distribution when Qij is arbitrary
This equation agrees with the numerical integration results to at
least ten decimal places; note that eq 31 reduces to eq 25 when
n, = 0.
The structural constants rfj, 111,and nufor CF31are summarized
in Table 1.36 The two-dimensional radial distribution curves
corresponding to the perpendicular/unexcited subset of CFJ are
presented in Figure 13. The isotropic pattern consists of three
rings: the inner ring corresponds to the C-F atom pairs, the
middle ring is an overlap of the C-I and the F-F atom pairs, and
the outer ring corresponds to the Fa-I atom pairs. A cross section
of this cylindrically symmetric pattern is shown in Figure 14. All
three rings are present in the pcrpendicular/unexcited distribution,
but now the amplitude of each ring varies with the angle 4. The
order in the molecular sample (imposed by the anisotropic
distribution) provides more structural information in the dif-
fraction pattern by separating the atom pair components as a
function of 4. The amplitude of the middle ring is approximately
half as large as the isotropic distribution because the C-I and the
Fa-F components are orthogonal. The C-I scattering contribution
should be similar to the molecular iodine pattern in Figure 7b;
since rc-I I rF-F (QF-F = goo), the contribution from F.-F atom
pairs is closer to the pattern in Figure 7a. The sum of the two
contributions leads to a complete ring at -2.15 A. The area of
a radial distribution curve peakis proportional to n&Zj/rij, where
nij is the number of identical atom pairs present in the molecule
and Zi b the atomic number of atom i. In many cases it would
be possible to idenfity the two components of the middle ring
because their maximum peak areas would be different, but in this
example it happens that 2~21- 328.It is still relatively simple
to identify the components, however, because the C-I interference
fringes are damped by the cos(qc - 71) phase term and the F-F
interference fringes are not damped. Consequently, the F-.F
peak is expected to be narrower and taller than the C-I peak, and
this is confirmed in the cross sections (Figure 14).
The perpendicular/unexcited radial distributions in Figure 13
and in the profiles of Figure 14 provide qualitative information
about the angles QC-F and &...I. A quick glance at the inner ring
shows that the C-F bond is almost orthogonal to the C-I bond
because the peak is larger on the x-axis than on the y-axis.
Conversely, the amplitude distribution of the outer ring shows
that Q F - ~ must be closer to Oo (or 180O) than 90°. It will be
possible to determine aij with great precision by carefully fitting
thex- and y-axis molecular scattering curves, and a more detailed
discussion of this process will be presented in future publications.
In X-ray crystallography, the entire structure of the unit cell
is mapped out by taking a series of diffraction patterns using
different crystal orientations. This process can be imitated in
UED to some extent by exciting different dipole transitions-the
perpendicular/unexcited radial distribution of CF31 will be
different if the excitation axis is parallel to a C-F bond. These
diffraction patterns thus contain information about the nature of
the excited transition (perpendicular versus parallel, etc.), in
addition to structural details.
Finally, rotational recurrence UED provides a unique oppor-
tunity for determining the rotational constants and structure of
radicals and other dissociation products. If the dissociation takes
place more quickly than the duration of the rotational recurrence,
then the dissociation products will have anisotropic spatial
orientation distributions. For example, CF31readily dissociates
into CF3 and atomic iodine when excited by a 266-nm laser pulse.
The Journal of Physical Chemistry, Vol. 98, No. 11, 1994 2775
Figure 12. Scattering geometry for a position vector ri, that is not parallel
to the excitationaxis. The excitation axis (2’) is defined by altitude angle
Q and azimuthal angle tj (see Figure 1). The angle between ru and I’
is Q,. The position vector sweeps out a circle in the primed coordinate
frame, where angle a is defined relative to the x’-axis. Calculation of
the scattering pattern rquires a triple-integration over a,tj, and Q. To
= ru co8 Q, and not at z’ 0.-
simplify the illustration, the x’and y’axes are shown intersecting at z’
TABLE 1: Structural Parameters for Trifluoromethyl Iodide
(Ref 36).
atom pairs no. r,lA hJlA Qijldeg
C-F 3 1.3314 0.0510 110.6
c-I 1 2.1409 0.0465 0.0
F-F 3 2.1535 0.0547 90.0
F--I 3 2.8916 0.08 12 154.5
a Internuclear separation, ru, mean amplitude of vibration, 11,; angle
between rij and C-I axis, Q,.
The CF3 radicals will take on a perpendicular/excited distribution
at each rotational recurrence; since the moment of inertia ofCF3
is not equal to the moment of inertia of CF31, the rotational
recurrence times of CF3 will be different (and resolvable) from
the parent species.
IV. Vibrational Coherence
In the previous section it was shown that additional structural
and spectroscopic information can be obtained by observing the
diffraction pattern of a laser-excited molecular sample during
rotationalrecurrences. The experimental factors that enable this
are the ultrafast laser pulse, which creates a coherent superposition
of rotational states, and the ultrafast electron pulse, which has
sufficient time resolution (a few picoseconds) to record the
diffraction pattern of the molecular sample during the rotational
recurrence window.
Here we investigate the electron scattering patterns from a
molecular beam sample with vibrational coherence. A femto-
second laser pulse creates the coherence, a superposition of
vibrational eigenstates. Traditionally, the time evolution of this
superposition, or wave packet, is monitored by a second femto-
second laser pulse with FTS to follow the molecular dynamics of
unbound, bound, and quasi-bound systems.17 We wish to show
that UED provides similar information about the dynamics and
potential energy surfaces of molecular systems; the simulations
presented are important to test two regimes for- structural
changes: coherent motion and the kinetic regime. UED may be
conducted even when little spectroscopic information is known
about the system-the probe involves only the state of interest,
and not a transition involving two states. Furthermore, the
dynamics along the reaction coordinate can be extracted for
complex systems because UED records all structural changes. In
1116 The Journal of Physical Chemistry, Vol. 98, No. I I , 1994
(a)
4.0 4.0
Internuclear Separation (A)
Figure 13. Two-dimensional radial distribution curves of CF& (a)
Isotropic sample. The inner ring wrresponds to the C-F separation, the
middle ring is a sum of the C-I and F-F separations, and the outer ring
wrresponds to the F-I separation. Only one quadrant is shown. (b)
Perpendicularfunexcited subset of the molecular sample after laser
excitation along the C-I band axis. Only one quadrant is shown. The
inner ring is most intense along thc x-axis because ~ G F is almost
perpendicular to rc.1. The outer ring is most intense along the y-axis
becauserF-Iisalmost parallel torc.1. The twocomponentsofthemiddle
ring have been separated along the x- and y-axes because rF.+ IrGI.
Scattering from TCI is found along the y-axis. This peak is less intense
than therp-Fpeakalong thex-axis becausescatteringfromrc-lisdamped
by thews(qc-s) term. Distortions in the baseline (seesection II1,part
D) actually exaggerate this effect. but it can still be ObseNed in the
corrected profiles (Figure 14)
this section we will comparethediffraction patterns from electron
pulse/velocity mismatch temporal resolutions (re)of both 50 and
500 fs. The experimental limit of time resolution is discussed in
the accompanying paper.21
The diffraction patterns are determined as a function of time
by calculating the electron scattering from classical trajectories
ofmolecular iodineexcited totheBstate. Asaresult,thissection
begins with a discussion of the scattering equations involved in
trajectory calculations, and the trajectory calculations themselves
are then described in part B. We discuss the diffraction patterns
when B-state iodine dissociates (part C) and when it is trapped
within the potential well (part D), and conclude this section by
examining the experimental applications of UED to molecular
dynamics studies on several different time.scales.
A. Theoretical Framework. To emphasize the role of vibra-
tional coherence in the diffraction patterns, we will ignore the
effects of anisotropic spatial orientation distributions in the
Williamson and Zewail
0 1 2 3 4
Internuclear Separation (A)
Figure 14. Radial distribution curve cross sections of isotropic CFjI and
of the perpendicularfunexcited CFjI subset. The curves have k e n
baseline-corrected to emphasize thechanges in each pcak (wmpare with
the uncorrected surface in Figure 13b). As discussed in the text, the C-I
and F-I pcaks arc most intcnse along the y-axis and least intense along
the x-axis. The C-F and F-F peaks are most intense along the x-axis.
scattering sample and assume that the excited molecules have an
isotropic distribution The diffraction patterns will therefore be
cylindrically symmetric and consist of sums of the zero-order
spherical Bessel function, jo. This will a m u n t for the rotational
averaging shown in eq 5 , but vibrational averaging must be
considered more carefully. Our classical trajectory calculation
consists of a molecular ensemble in which the initial conditions
of each trajectory are randomly determined with a Monte Carlo
technique according to some probability distribution, The total
number of trajectories, NT. must he sufficiently large such that
the macroscopic behavior emerges by averaging the behavior of
the individual trajectories. Consequently, if the molecular
scattering curve is calculated from a large numberoftrajectories,
than the total scattering should automatically a m u n t for
vibrational averaging.
Themolecular scattering intensity fromaset ofNTtrajectories
for molecular iodine simplifies to
where r.(f) is the evolution of the internuclear separation of the
nth trajectory in time. Two-dimensional diffraction plots with
the modified molecular scattering along the abscissa (in A-I) and
time along the ordinate (in fs) will be created. Generating radial
distribution curves from these plots is straightforward.
B. Molecular Dynamics Calculations. With molecular dy-
namics simulations of solutions, Bergsma et al. have shown the
calculated Vibrational dynamics of iodine in different solvents
following X-ray diffraction.'6 Here, the trajectory calculation
was designed to mirror the UED experimental excitation process,
where the pump laser excites isolated molecular iodine, creating
a wave packet whichevolvesin timeon theB state. Thisevolution
was recorded for each trajectory inaone-dimensional array,r.(f),
and the diffraction pattern at a specific time 1, was obtained by
summing the scattering contributions from all rn(f,) (eq 32). We
wish to compare the diffraction patterns from several different
excitation energies, 2000,3000, and 4000 cm-I, which are below
the dissociation energy, and a t 4750 cm-I, which is above the
dissociation energy. These energies are relative to the bottom of
the B-state potential
One thousand trajectories were used for the bound systems,
and tenthousandtrajectorieswereusedforthedissociativesystem.
It wasassumed that theinitialground-state molecular iodinewas
Ultrafast Electron Diffraction
(a) ,
I
I ~ .
..~~
~
i
\-._
s (A') - 10
Internuclear 10
Separation (A)
Figure 15. Molecular dynamics of B-state iodine excited to 4750 cm-I
above the bottom of the potential well. Iodine dissociates at this energy.
Electron pulse temporal resolution: r. = 50 fs. (a) Modified molecular
scattering curve as a function of time. (b) Radial distribution curve as
a function of time. The hump at 400 fs appears because the wave packet
slows dawn as it climbs the outer potential wall before dissociation.
vibrationally cold, with the initial energy and probability
distributions corresponding to Y = 0. The excitation laser pulse
had a Gaussian temporal profile (fwhm = 50 fs), and the energy
bandwidth was determined by assuming that the pulse was
transform limited.
The goal of the trajectory calculation was to generate a two-
dimensional array containing internuclear separation probabilities
as a function of time. The size of each position element was 0.01
A and the size of each temporal element was 5 fs. The initial
conditions of each trajectory were determined using the Monte
Carlo technique. The initial energy was equal to the excitation
energy (e.&, 3000 cm-I) plus an offset determined by the laser
bandwidth, and the initial position was determined from the
probability distribution ofground-stateidine. Several iterations
were sometimes necessary to establish a valid combination of
initial energy and position, particularly a t lower energies where
the Franck-Condon overlap between the X state and the B state
is poor. The initialvelocitywas calculated from the initial energy
and the B-state potential surface, and a randomly determined
direction for the velocity (Le., bond contracting or expanding)
was assigned.
After defining the initial conditions, the evolution of each
trajectory on the B-state potential surface was calculated. The
program employed a Hulburt-Hirschfelder potential energy
surface" with Dunham coefficients provided by Gerstenkorn and
The Journal of Physical Chemistry, Vul. 98. Nu. 11,1994 2111
0 2 4 6 8 1 0
Internuclear Separation (A)
Figure 16. Molecular dynamics of B-state iodine excited to 4750 Em-'
above the bottom of the potential well. Iodine dissociates at this energy.
Electron pulsetemporal resolution: 7. = 500 fs. (a) Modified molecular
scatteringcurveas a functionof time. Theascillationsdampoutquickly
because of the low temporal resolution. (b) Comparison of the radial
distribution CUNS after I ps for = 50 fs and 7, = 500 fs. The radial
distribution C U N ~at time zero ( T ~= 50 fs) is shown as a refercnce.
L ~ c . 3New
~ positions and velocities were calculated every 5 fs
using an embedded Runge-Kutta integration scheme designed
to conserve the total energy of each traject0ry.3~The calculation
began a t 4 . 5 ps (with the static ground-state distribution) and
continued out to +2.5 ps. The zero of time, f = 0, corresponded
to excitation of the molecular sample with the pump laser.
Theduration of the pumplaser pulse was included by offsetting
time zero for each trajectory by a random amount determined
witha MonteCarlotechniqueon thepumplasertemporal profile.
Prior to to.., the two-dimensional array was filled with the
probability distribution ofground-state iodine normalized to unit
area. Evolution of the trajectory after was modeled by adding
one to the array element corresponding to the current time and
calculated position.
The temporal profile of the electron pulse (including velocity
mismatch effects) was assumed to be Gaussian. The duration of
the electron pulse was included in the calculation by convoluting
the temporal behavior of a specific internuclear distance (one
row in the array) with the temporal profile of the electron pulse.
The final result was an array of internuclear distances ranging
in time from 0 to 2 ps. The modified molecular scattering curve
was calculated from 0 to 15 A-' (in 0.02-A--1 steps) at each time
interval using eq 31, and the radial distribution curve was
calculated from sM(s) with kd = 0.01 A2.
2118 The Journal of Physical Chemistry, Vol. 98, No. 11. 1994
(a) 1
, ._
-.__
, ..
'-,
'
..
Internuclear
Separation (A)
(c)
-.
.
1-
//
,/
Internuclear
Separation (A)
Figure 17. Molecular dynamics of B-state iodine excited below the dissociation energy (4381.8 cm-I): (a) 2000 cm-'. = 50 fs; (b) 3000 cm-', 1.
= 50 fs; (c) 4000 cm-1, *I = 50 fs; (d) 4000 cm-1, . T =
~ 500 fs. In all graphs, the peak intensity at the inner and outer turning pints decreases as a
function of time, which shows that the classical wave packet is spreading and approaching a Static distribution.
C. Above theDissociationEnergy. The first systemof interest
was iodine excited to 4750 cm-1 above the bottom of the B-state
notentialwell. ThedissociationthresholdoftheB-stateislocated
at 4381.8 cm-l, and it is expected that the diffraction patterns
will reflect a continuous increase in the internuclear separation
of the molecule with time. The modified molecular scattering
curve and radial distribution curves with re = 50 fs are presented
in Figure 15. The radial distribution curve shows that iodine
molecules traverse the potential well within the first 500 fs and
subsequently dissociate. The position of the radial distribution
peak increases in distance with time, and the peak also flattens
out as the wave packet gradually disperses across the potential
surface. The modified molecular scattering curve presents the
same information, but in the inverse-distance domain. The
frequency of oscillation increases with time as 11.1 increases. The
amplitude of the oscillations diminish rapidly as the wave packet
spreads; scattering contributions from a wide range of internuclear
separations lead to a low scattering intensity.
The calculated behavior of iodine is similar to observations of
dissociating I2 and ICN made with FTWMand to the corres-
ponding quantum mechanical wave packet calculations of the
FTS ex~eriment.".~2 UED Drovides the actual dvnamical
trajectory of the fragments. Aiso, by taking diffraction patterns
at various times after laser excitation and calculating the change
in the internuclear separation, it would he possible to determine
the kinetic energy distribution of the fragments and deduce the
dissociation energy. Such measurements require femtosecond
time resolution, however, as is shown by the molecular scattering
Williamson and Zewail
Internuclear
Separation (A)
(d) L.\\..,.
-. 1..
...~.
\~
Internuclear
Separation (A)
$I
curve for re = 500 fs in Figure 16a. The interference fringes
are almost completely washed out after the first 400 fs and the
-
molecularscatterineintensitvisvervsmall. Acomoarison ofthe
radial distribution curves a t 1 ps for re = 50 fs and re = 500 fs
(Figure 16b) shows that the peak flattens significantly as the
temporal resolution changes by an order of magnitude.
D. Below the Dissociation Energy. We also performed
moleculardynamicscalculationsfor idineatthreeenergies (2000,
3000,and4000c11-~)below thedissociationenergyoftheB-state.
The radial distribution curves are plotted as a function of time
in Figure 17. When the temporal resolution is high (7. = 50 fs),
thevibrational motion is clearly present, even for fast oscillations
at 2OOOcm-1. Closeexamination shows thatvibrationaldephasing
occurs, and one can expect that vibrational quantum coherence
would be apparent if a quantum mechanical wave packet
calculation was conducted. As with FTS,a Fourier analysis of
this oscillatory motion would yield the spacing between the
Vibrational energy levels.41
The oscillation period a t 4000 cm-I is long enough that the
vibrational motion may still be resolved when re = 500 fs (Figure
17d). although there appears to be rapid dephasing. The
vibrational motion a t lower energies is not resolved, and the
diffraction pattern is static after t h e first 500 fs. This static
pattern represents a weighted sum of the position probability
amplitudes of the vibrational states excited within the laser
bandwidth, and therefore these diffraction patterns are useful
for determining the shapeofthe potentialenergysurface. Figure
18 shows the 2-ps radial distribution functions (with rC= 500 fs)
Ultrafast Electron Diffraction
5000
I
4000
c
E 3000
2 0I
*
w
r
C
2000
1000
+--c--cI
1 2 3 4 5 6
Internuclear Separation (A)
Figure 18. Radial distribution curves at 2 ps from molecular dynamics
of B-state iodine excited below the dissociation energy. The RD curves
are shown superimposed over the B-state potential energy surface.
Electron pulse temporal resolution: T~ = 500 fs. At this temporal
resolution, the trajectories for 2000 and 3000 cm-l are static after the
first 500 fs, although vibrational oscillations of B-state iodine molecular
dynamics at 4000 cm-I may still be resolved (see Figure 17d).
for all three energies overlaid on the B-state potential energy
surface. Note that the curves for 2000 and 3000 cm-1 are static
and represent the average vibrational motion, but the 4000 cm-1
curve is still evolving in time. This type of experiment has no
need of ultrafast time resolution and is actually better suited to
longer time scales in which the bandwidth of the excitation laser
is narrow enough to pick out specific vibrational states-state
selective diffraction.
E. Experimental Applications to More Complicated Systems.
Here, we discuss ways UED might be applied to dynamical
experiments where reaction intermediates are formed on longer
time scales. The most important characteristic of gas-phase
electron diffraction is that the scattering patterns are extremely
sensitive to small changes in internuclear separation. Conven-
tional GED experiments typically report internuclear separations
to within 0.005 or less;4 so far, a limited range of s is detected
inUED(lSA--',asopposedto -4OA-linGED),andtheprecision
is more on the order of 0.05 A. This sensitivity is still sufficient
to distinguish between different vibrational states (Figure 18) as
well as between different electronic states (Figure 8). UED
therefore provides another detection scheme for monitoring
ultrafast decay processes, either when the products dissociate or
when they merely change to a different vibrational or electronic
state, Such an avenue of detection is, of course, particularly
useful when spectroscopic data about higher excited states is not
available or is too complicated.
As an example of how UED might be applied to dynamical
studies, we can consider the three-body photofragmentation
process of CzF412 studied in real time.43 The photofragmentation
is a two-step process in which both iodine atoms dissociate, leaving
tetrafluoroethylene
-
'I
C2F412* C2F41* I* + (33)
'2
C2F41*+ F2C=CF2 +I (34)
The primary C-I bond breakage is very fast ( r l 5 0.5 ps), while
the secondary bond breakage results from internal energy
redistribution and is significantly slower (72 = 32 ps at a given
energy). The dynamics of the two steps depended on the total
energy and were probed by measuring the rises of excited-state
atomic iodine (I*) and ground-state atomic iodine (a biexpo-
The Journal of Physical Chemistry, Vol. 98, No. 1I, 1994 2779
M 4 0 6 0 8 0 1 0 0 I
Time (DS)
Internuclear - 5 6
Separation (A)
Figure 19. Reaction dynamicsof CzF412. Thefirst iodine atom dissociates
directly with 71 I0.5 ps. The second iodine atom dissociates with 7 2 =
32 ps. (a) Ground-state iodine atom signal as a function of time (ref 43).
(b) Radial distribution curve as a function of time. At time zero the
molecular sample is pure C2F412. After time zero the molecular sample
is a mixture of C2F.J radical and F2C=CF2. The composition was
obtained from the experimental results for 71 and 72.
nential; see Figure 19a). The corresponding time evolution of
theradialdistributioncurveisshowninFigure 19b. Themolecular
scattering curve is simply a weighted sum of the three components
(C2F412, C2F41,and F&=CF2); the composition of the molecular
sample was calculated as a function of time using measured values
of T~ and 72. Structural parameters for C2F4I2 and F2C==CF2
were obtained from the l i t e r a t ~ r e ~and
~ pthe
~ ~structure of the
radical component was assumed to be identical to C2F4I2 with
one iodine atom missing.
The radial distribution curve clearly reveals the dynamical
changes of the fragmentation process. The primary bond breakage
is shown by the rapid disappearance of the peak at 5.0 A, which
corresponds to the I-.I internuclear separation. The subsequent
transformation of the radial distribution curve over the next 100
ps characterizes the secondary bond breakage; note that the
intensity of the first peak at 1.3 A (C-C, C-F) does nor change
because all carbon and fluorine atoms remain in the molecule,
although the position of the peak shifts inward slightly as the
C-C bond changes to a double bond. The ability of UED to
monitor this type of dynamical change has already been
demonstrated19 and is detailed in the accompanying paper.2'
The primary and secondary bond breakages in C2F4I2 are very
different processes and help illuminate the distinctions between
monitoring vibrational coherence versus following dynamical
decays. Loss of the first iodine atom is a direct process and very
fast; if the molecule is excited with a femtosecond laser pulse, a
wave packet is formed on the dissociative potential energy surface.
With a 50-fs electron pulse, it would be possible to monitor this
dissociation process in time, and the diffraction patterns would
be similar to those shown in Figure 15. The 1-1 separation would
rapidly move outward from 5.0 A, and one set of C-I, C-I, and
Fa-I peaks would shift outward as well. Loss of the second iodine
atom, however, is not a coherent process. The individual C2F41
radicals dissociate independently of each other, with the behavior
of the entire population characterized by the decay constant 7 2 .
Trajectory calculations are unnecessary to model this type of
dynamical process because the loss of the second iodine is very
fast compared to the uncertainty in the onset of the dissociation.
2780 The Journal of Physical Chemistry, Vol. 98, No. 11, 1994 Williamson and Zewail

TABLE 2: Summary of Spatial Scattering Functions F, for Several Spatial Orientation Probability Distributions fin,$) Where
n,= 0.
spatial orientation fraction of
distribution molecules P(Q,+) Fij(5)

isotropic 1 1 Jo[sr,jl

parallel excited '13 cos2 a

parallel unexcited 2/ 3 sin2 Q

perpendicular excited 'I3 sin2 f? cos2 +

perpendicular unexcited 2 13 1- sin2Q cos2 +

unpolarized excited 1 - sin2Q sin2IL

unpolarized unexcited Ii3 sin2 f? sin2 +

perpendicular excited
S'ij
- (
sin2 Qij + (2-3 sin2 Q,j)

The bottom row shows the functional form of the perpendicu1arJexcited Fij for arbitrary

Thus the diffraction pattern may be calculated as a sum of acknowledges the National Science Foundation for providing a
scattering from each of the three components weighted by their Graduate Student Fellowship.
relative populations.
Appendix
V. Conclusion Many of the definite integrals generated from eq 17 are not
readily available in mathematical references. This appendix
Debye's work on X-ray diffraction showed that the scattering provides a general description of the integration process needed
pattern from a gas is rich with structural information, despite the to obtain the closed form solutions summarized in Table 2.
randomness in the position and orientation of the molecular Integration of eq 17 over J, is accomplished with one of the
sample. One focus of this paper was to show that ultrafast following identities:
preparation and ultrafast electron diffraction can be used to
introduce and observe order in gas phase samples, thus yielding
a new dimension in molecular structure analysis. The formation
of a coherent superposition of rotational and vibrational eigen-
states, which can be controlled by the experimental time delay, or
are transient impositions of this order on an otherwise isotropic
sample. Rotational recurrence UED provides a detailed structural (A-2)
picture of the ground-state species: internuclear distances,
moment of inertia (from the rotational constant), and bond angles.
Vibrational coherence studies reveal transition-state dynamics where y is defined by
and provide a map of the potential energy surface; this information
is very similar to results from FTS. Applications were discussed y = (A2 + B2)'/* ('4-3)
for small systems (two atoms), more complex systems (five or
eight atoms), and reactions involving direct dissociation or reactive Equation A-1 may be verified by expanding the exponential as
intermediates. The following paper details our apparatus, its a series and employing definite integrals listed in Gradshteyn
temporal and spatial resolutions, and experimental applications. and Ryzhik.468 Equation A-2 may be verified by expanding the
exponential, expanding each term in the exponential sum, and
Acknowledgment. This work was supported by a grant from integrating term by term.6b As anexampleof how theseidentities
the U S . Air Force Office of Scientific Research and the National are applied, eq A-1 simplifies F',,for the isotropic distribution to
Science Foundation. The authors thank Dr. Scott Kim and Dr.
Marcos Dantus for their stimulating discussions on ultrafast F,,(s) = iJ:sin R Jo[ sr cos sin R] eisrsin(e/2)oos*
dR (A-4)
electron diffraction, and Hakno Lee and Dr. Juen-Kai Wang for 2
their help. We thank Dr. Ralf Friichtenicht for assisting in the The final closed form is obtained by integrating over R using
translation of some of the referenced (German) articles. J.C.W. one of the following identities:
Ultrafast Electron Diffraction
Jor(sin (p)"+'J,,[Bsin v]eiAcoscP
dv = 2 --j,[y]
B" (A-5)
Y (14) Elsayed-Ali, H. E.; Herman, J. W. Reo.Sci. Instrum. 1990,61,1636.
or
Jorcos2 cp(sin cp)"+'J,[B sin cp]eAmcPdv =
These integrals may be verified by expanding the Bessel function
as a series and making a change of variables to t = cos cp.
Integration over t generates another Bessel function,* which is
also expanded. The double expansion that results for eq A-5 is
and the double sum for eq A-6 is similar. The final step is to
change the summation limits by defining i = m k and j = k +
Summation over j leads to a y2i term, and the sum over i
corresponds to the final Bessel function.
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