Vibrations of Polyatomic molecules
For a molecule with N atoms, the number of coordinates
required to specify the position of all the atoms is 3N.
These 3N displacements can be thought of in terms of
various degrees of freedom.
Translational : 3
Rotational : 2 for linear and 3 for nonlinear molecule.
Vibrational : 3N 5 for linear and 3N 6 for nonlinear
molecule.
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Normal modes of vibrations
Description of vibration most convenient and simple in terms of
normal modes.
Normal mode Collective, independent, synchronous motion of
group of atoms, that may be excited without exciting any other
mode.
Each normal mode may be approximated as a harmonic
oscillator with a characteristic frequency and an effective mass.
Any arbitrary displacement may be expressed as a superposition
of the normal modes.
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Vibrational spectroscopy
Actual (total) stretching motion
Independent components
contributing to the motion
(Normal modes): symmetric and
asymetric stretching
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Normal modes of water
Symmetric
stretch
Asymmetric
stretch
Bend
4
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Normal modes of CO2
5
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Normal modes of CO2
Symmetric stretch
inactive.
Asymmetric stretch
active, parallel bands.
Bends active,
perpendicular bands.
Two such modes
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Vibrational Raman spectra of diatomic
molecules
Gross selection rule: Molecular polarizability must
change during vibration.
The polarizability of a molecule is a measure of the
extent to which an applied electric field can induce an
electric dipole moment ( = E).
All diatomics are vibrationally Raman active.
Specific selection rule: =
Vibrational Raman spectra of diatomic
molecules
Specific selection rule: =
= +: Photons are scattered with a lower frequency than
that of the incident light, the Stokes lines.
= -: Photons are scattered with a higher frequency than
that of the incident light, the anti-Stokes lines.
Stokes lines are much more intense than anti-Stokes, because
very few molecules are in an excited vibrational state initially.
8
Vibrational Raman spectra of polyatomic
molecules
Gross selection rule: Normal mode motion must be
accompanied by a changing polarizability.
Very difficult to tell by inspection when this is so.
CO2: Symmetric stretch active, alternatively swells and
contracts the molecules. Motion changes its polarizabilty. The
mode is Raman active. Other modes (asymmetric stretch and
bending) are Raman inactive.
Useful Rule: If a molecule has a center of symmetry, no mode
can be both ir and Raman active.
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Vibrational spectroscopy
Infrared spectroscopy powerful tool in identifying
organic molecules.
Some modes essentially motions of individual
functional groups.
Others are collective motions of the molecule as a
whole fingerprint region of spectrum.
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Vibrations in polyatomic
molecules
Linear/angular
vibrations:
stretching/bending
Total vibrational motion
becomes more and more
complex as the number of
atoms increases
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Vibrational (IR) spectroscopy
Absorption frequency:
= 1/2 (k/1/2 where = mAmB/(mA + mB) is the
reduced mass and k is force constant
Typical range : 1013 1014 Hz ~ 102 103 cm-1
(Infrared region)
Hence, vibrational (absorption) spectroscopy is also
known as IR spectroscopy.
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IR frequency calculation
Absorption frequency:
(cm-1)= (k/1/2 /2c
C-H: k ~ 494 Nm-1; (~ 3000 cm-1)
N-H: k ~ 642 Nm-1; (~ 3400 cm-1)
O-H: k ~ 726
Nm-1;
(~ 3600 cm-1)
C=C: k ~ 972
Nm-1;
(~ 1650 cm-1)
CC: k ~ 1650
Nm-1;
(~ 2150 cm-1)
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IR frequencies of functional groups
Here the effect is mainly due to bond strength
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Factors affecting absorption
frequency
Absorption frequency:
Increases with increase in % of s character: sp3<sp2 <sp
e.g. C-H stretching frequencies:
< 3000 cm-1 for sp3, >3000 cm-1 for sp2, ~3300 cm-1 for sp
Decreases on increase in conjugation
e.g. In aldehydes, ketones and esters, C=O stretching frequency
decreases by 25~30 cm-1 when conjugated with C=C
Is affected by inductive/resonance/electromeric effects
Decreases due to hydrogen bonding
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Modes of vibration
Symmetric stretching
Scissoring
Wagging
Asymmetric stretching
Twisting
Rocking
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IR frequency data
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IR frequency data
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Interpreting IR spectra
C=O is highly sensitive to its environment
EACH DIFFERENT KIND OF C=O COMES AT A DIFFERENT FREQUENCY
acid
chloride
ester
aldehyde
ketone
carboxylic
acid
amide
RC
RC
RC RC RC
RC
O
R
'
C
l
H
N
H
R
O
H
2
1800
1735
1725
1715
1710
1690
anhydride
RCO
CR
1810 and 1760
BASE
VALUE
THESE VALUES ARE
WORTH LEARNING
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Interpreting IR spectra
O
O C=O at 1725 cm-1
R C
also look for aldehyde CH
H
2850 and 2750 cm-1
O
R C
N H
H
R C
O
O
C=O at 1690 cm-1
also look for two
NH peaks at
3400 cm-1
R C
C=O at 1710 cm-1
also look for OH
H (H-bonded) and
C-O ~1200 cm-1
C=O at 1735 cm-1
also look for two
O R' C-O at 1200 and
1000 cm-1
Ketones have C=O at 1715 cm-1 and no NH, OH, C-O or -CHO
Anhydrides have two C=O peaks near 1800 cm-1 and two C-O
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Interpreting IR spectra
C-H stretching frequencies:
<3000 cm-1 for sp3; >3000 cm-1 for sp2; ~3300 cm-1 for sp3;
Doublet at 2710~2810 cm-1 for aldehydic C-H stretch
Methylene and methyl C-H stretching:
~2850 cm-1 (sym); ~2962 cm-1 (asym)
CH2 bend
CH3 bend
Hexane
CH3
-CH2(C-H stretch) (C-H stretch)
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Interpreting IR spectra
Toluene: Ar-H, CH2-H, C=C
Ar-H
CH3
CH3
C=C
benzene
C-H bending
monosubstituted
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Interpreting IR spectra
O-H stretching: ~3600 cm-1 for alcohols;
brodens and lowers to 3300 cm-1 due to H-bonding in alcohols, acids, etc.
How to distinguish between intramolecular and intermolecular H-bonding?
OH
O-H
H-bond
CH2
C-O
C-H
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Interpreting IR spectra
Butanoic acid:
Concentrated acid gives broad peak for OH stretch which disappears on dilution
The C-H stretching peak is superpositioned.
Note the peaks for C=O stretch; C-O stretch and the H-C-H bending (methylene)
O-H
H-bond
C-O
CH2
C-H
C=O
CH3 CH2 CH2 C
OH
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Interpreting IR spectra
N-H stretching frequencies: 3300-3400 cm-1
Doublet for primary amines (sym, asym stretch) ; single peak for secondary amines
Bending modes:
Bending frequency for primary amines > bending frequency for methylene Why?
NH2
scissor
NH2
CH3
CH2
CH3 CH2 CH2 CH2 NH2
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Interpreting IR spectra
CN stretching: 2250 cm-1 (strong peak)
CC stretching: 2150 cm-1 (medium peak)
=
C=N
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Interpreting IR spectra
Typical example: Nonanal (aldehyde)
C=O stretch at 1730 cm-1;
aldehydic C-H (stretch doublet) 2859 and 2717 cm-1;
CHO
CH bend
C=O
O
CH3 CH2 CH2 CH2 CH2 CH2 CH2 CH2 C
Note the intense doublet at 2929 and 2859 cm-1 because of alkyl C-H stretch
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