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Molecular Spectroscopy
Light has magnetic and electric components
-oriented at 90
-can be polarized
General Terms
Frequency, , is the number of oscillations of the field that occurs
per second
Wavelength (): The linear distance between any two equivalent
points on successive waves (e.g. successive maxima or minima)
Velocity of propagation (v): frequency in cycles per second
wavelength in meter per cycles
Velocity of radiation depends on the composition of the medium
- Reciprocal of the wavelength in cm1, equal to
Wavenumber ():
k where k is proportionality constant
Electromagnetic Spectrum
X-ray:
core electron
excitation
300 kJ/mol
UV: valance
electronic
excitation
IR: molecular
vibrations
Radio waves:
Nuclear spin states
(in a magnetic field)
170 kJ/mol
Quantum Transitions
UV-vis region
bonding electrons
Atomic Absorption
UV-vis region
FT-IR
IR/Microwave
vibrations, rotations
Raman
IR/UV
vibrations
FT-NMR
Radio waves
X-Ray Spectroscopy
X-rays
X-ray Crystallography
X-rays
3-D structure
UV-vis region
Quantitative analysis/
Beers Law
Atomic Absorption
UV-vis region
Quantitative analysis
Beers Law
FT-IR
IR/Microwave
Raman
IR/UV
FT-NMR
Radio waves
X-Ray Spectroscopy
X-rays
Elemental Analysis
X-ray Crystallography
X-rays
Structure determination
Different Spectroscopies
UV-vis electronic states of valence electrons/
d-orbital transitions for solvated transition metals
Fluorescence emission of UV/vis by certain molecules
FT-IR vibrational transitions of molecules
FT-NMR nuclear spin transitions
X-Ray Spectroscopy electronic transitions of core
electrons
Molecular Spectroscopy
Absorption
Types of Transitions
In alkenes, only and bonds. So, only , and *, * Mos are present
But amines, ketones, aldehydes & halides have N, O, X and lone pairs on it.
So we need to consider them as non-bonding electrons (n) in the MOs.
Types of Transitions
* and * transitions: high-energy,
accessible in vacuum UV (max <150 nm). Not usually
observed in molecular UV-Vis.
n * and * transitions: non-bonding
electrons (lone pairs), wavelength (max) in the
150-250 nm region.
n * and * transitions: most common
transitions observed in organic molecular UV-Vis,
observed in compounds with lone pairs and multiple
bonds with max = 200-600 nm.
Any of these require that incoming photons match in
energy the gap corresponding to a transition from
ground to excited state.
Energies correspond to a one photon of 300 nm light
are ca. 95 kcal/mol
Example for to *
In alkenes, only and bonds. So, only , and *, * MOs are present
Conjugated Polynenes
*;max=218
=11,000
n*;max=320
=100
HowDoUVspectrometerswork?
Matchedquartzcuve9es
Sampleinsolu@onatca.105M.
SystemprotectsPMtubefrom
straylight
D2lampUV
TungstenlampVis
DoubleBeammakesita
dierencetechnique
P0
(powerin)
Absorbance:
A=log10T=log10P0/P
P
(powerout)
TheBeerLambertLaworBeersLaw:
A=cl
WheretheabsorbanceAhasnounits,sinceA=log10P0/P
isthemolarabsorb@vitywithunitsofLmol1cm1
listhepathlengthofthesampleincm
cistheconcentra@onofthecompoundinsolu@on,expressedinmolL1(orM,molarity)
(Blue shift)
(Red shift)
Color Wheel
max
253239
256
248
20,300 cm1
Reddish Violet
Wavelength (nm)
GS
ES
d-d Transition
IR Spectroscopy Basics
IR Spectroscopy Basics
IR Spectroscopy
Molecular Motions
Notethehighwavenumber(highenergy)requiredtoproducethese
mo@ons.Thebendingmo@onsaresome@mesdescribedaswaggingor
scissoringmo@ons
Each of these two main types of vibration can have variations. A stretch
can be symmetric or asymmetric. Bending can occur in the plane of the
molecule or out of plane; it can be scissoring, like blades of a pair of
scissors, or rocking, where two atoms move in the same direction.
Different stretching and bending vibrations can be visualized by
considering the CH2 group in hydrocarbons. The arrows indicate the
direction of motion. The stretching motions require more energy than the
bending ones.
You can see that the lower wavenumber values are consistent with lower energy to
cause these vibrations.
A molecule absorbs a unique set of IR light frequencies. Its IR spectrum is often
likened to a person's fingerprints. These frequencies match the natural vibrational
modes of the molecule. A molecule absorbs only those frequencies of IR light that
match vibrations that cause a change in the dipole moment of the molecule. Bonds in
symmetric N2 and H2 molecules do not absorb IR because stretching does not change
the dipole moment, and bending cannot occur with only 2 atoms in the molecule. Any
individual bond in an organic molecule with symmetric structures and identical
groups at each end of the bond will not absorb in the IR range. For example, in
ethane, the bond between the carbon atoms does not absorb IR because there is a
methyl group at each end of the bond. The C-H bonds within the methyl groups do
absorb.
IR Spectroscopy Basics
Frequency Range:
OH
CH
CH3CH2OH
NH
CH
CCstretchappearsat2250,CHat3000
CC
CH
Me
Me
CH
CN
CH3CN
CH
C=O
C=C
CH
WhatIRpeakswouldyouexpectforthetwomoleculeswiththeformulaC2H6O?
Ethanol
Dimethylether
OH32003400cm1(broad) CH3000cm1
CH3000cm1
CO10601150cm1
CO10601150cm1
IR Spectrum of Octanal
The spectrum for the aldehyde, octanal (CH3(CH2)6CHO), is shown here. The most
important features of the spectrum are carbonyl CO stretch near 1700 cm-1 and the CH
stretch at about 3000 cm-1. If you see an IR spectrum with an intense strong band near
1700 cm-1 and the compound contains oxygen, the molecule most likely contains a
carbonyl group,
Lookforindica@onsthatanOHisalsopresent.Ithasabroad
absorp@onnear33002500cm1.ThisactuallywilloverlaptheCH
stretch.TherewillalsobeaCOsinglebondbandnear11001300
cm1.Lookforthecarbonylbandnear17251700cm1.
ESTER
LookforCOabsorp@onofmediumintensitynear1200cm1.There
willbenoOHband..Lookforthecarbonylbandnear17351750cm1
ALDEHYDE
LookforaldehydetypeCHabsorp@onbands.Thesearetwoweak
absorp@onstotherightoftheCHstretchnear2850cm1and2750
cm1andarecausedbytheCHbondthatispartoftheCHOaldehyde
func@onalgroup.Lookforthecarbonylbandaround17401720cm1.
KETONE
TheweakaldehydeCHabsorpFonbandswillbeabsent.Lookforthe
carbonylCObandaround17251705cm1.
If no carbonyl band appears in the spectrum, look for an alcohol O-H band.
ALCOHOL
LookforthebroadOHbandnear
36003300cm1andaCOabsorp@onband
13001000cm1.
near
IfnocarbonylbandsandnoOHbandsareinthespectrum,checkfordoublebonds,C::C,from
anaroma@coranalkene.
ALKENE
Lookforweakabsorp@onnear1650cm1foraC=C.Therewillbe
aCHstretchbandnear3000cm1.
AROMATIC
Lookforthebenzene,C=C,doublebondswhichappearas
mediumtostrongabsorp@onsintheregion16501450cm1.
TheCHstretchbandismuchweakerthaninalkenes.
Ifnoneofthepreviousgroupscanbeiden@ed,youmayhaveanalkane.
ALKANE
Themainabsorp@onwillbetheCHstretchnear3000cm1.Thespectrumwillbesimple
withanotherbandnear1450cm1.