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Vibrational Spectroscopy

Vibrational Motion: Molecular Calisthenics


Harmonic oscillator
( )
e
F k r r =
14
1
2 10
vib
s t
v

= ~
A molecule vibrates ~50 times during a molecular
day (one rotation)
Quantization of Vibrational Energy
By solving Schrodinger equation for vibrational motion,
Vibrational energy level
Zero point energy
Spacing between adjacent vibrational sates
where is a vibrational quantum number
Vibrational Spectra
Molecules are not Static
Vibration of bonds occurs in the liquid, solid and gaseous phase
Vibrating Energy Frequency (and the appropriate frequencies for molecular vibrations
are in the Infrared region of the electromagnetic spectrum
Vibrations form therefore, a fundamental basis for spectroscopy in chemistry--the bonds are
what makes the chemistry work in structure and function
For Organic Chemistry the most important uses of these vibrations is for analysis of:
functional groups
structural identity, fingerprinting
What Kind of vibrations are These?
Bonds can.
Stretch
Bend
Wag
(rock)
These can number into the hundreds.
Some are symmetrical, some
antisymmetrical and many are coupled
across the molecule
Can be calculated. One easy
approximation is:

k
12
10 3 . 5

=
2 1
2 1
m m
m m
+
=
The reduced mass where m
1
, m
2

are the masses on either side of
vibration
k is the force constant, like the
Hookes Law restoring force for a
spring. Known and tabulated for
different vibrations
The Fundamentals
R
R
H
H
R
R
H
H
R
R
H
H
R
R
H
H
R
R
H
H
R
R
H
H
antisymmetric symmetric
rocking scissoring
in-plane
bending
stretching
out-of-plane
bending
wagging twisting
These oscillating electric
dipoles match in frequency
the incoming e-field
oscillations of IR light.
All the simple possibilities.
For n atoms in a molecule;
Linear: 3n 5 modes
Non-linear: 3n 6
modes
Example for a
methylene,given n=3
While useful, this
oversimplifies, since
molecular orbital picture
requires that atoms
cant vibrate without
affecting the rest of the
molecule.

Degrees of Freedom:
Translation, Rotation, and Vibration






Consider a single Ar atom moving in 3-D space:

- Moving motion is referred to as Translation
- To analyze the translation of an Ar, we need to know
position (x, y, z) and momentum (p
x
, p
y
, p
z
)
Where it is Where it is headed

- Each coordinate-momentum pair [for example, (x,p
x
)] is referred to as a Degree of
Freedom (DF)

- An Ar atom moving through 3-D space has three DFs

N argon atoms possesses 3N DFs:
All translational DFs
Center of Mass (Balanced
Point)
- A point mass that can represent the
molecule
- Motion of the center of mass requires 3 DFs
to describe it
- In general, regardless of its size or
complexity, a molecule has 3 translational
DFs
- Thus, (3N 3) DFs for the internal motions
of rotation and vibration
Rotational and vibrational
DFs
N atomic
Linear
Molecule
N atomic
Non-Linear
Molecule


Rotation

2 DFs

3 DFs

Vibration

3N 5

3N - 6

Vibrational Spectroscopy
Vibrational selection rule
1
1 ( )
1 ( )
absorption
emission
u
u
u
A =
A = +
A =
A Functional Group Chart
O-H str
NH str
COO-H
=C-H str
C
sp3
-H
C-H
-(C=O)-H
CN
CC
C=O
-C=N
-C=C
phenyl
C-O
C-N
F C-X
4000 3600 3200 2800 2400
2000 1600 1200 800 group
Br
Cl
Regions of Frequencies
Near -to
visible- IR
(NIR)
Combination
bands
3.8 x 10
14

to 1.2
x 10
14

12800 to 4000 0.78 to 2.5
Mid Infrared
Fundmental
bands for
organic
molecules
1.2 x 10
14

to 6.0
x 10
12


4000 to 200 2.5 to 50
Far IR
Inorganics
organometallics
6.0 x 10
12

to 3.0
x 10
11


200 to 10 50 to 1000
Spectral Region Frequency(Hz) Wavenumber(cm
-1
) Wavelength (,m)
Looking at a Spectrum
Divide the spectrum in to two regions:
4000 cm
-1
1600 cm
-1
most of the stretching bands, specific functional
groups (specific atom pairs). This is the
functional group region.

1600 cm
-1
400 cm
-1
Many band of mixed origin. Some prominent bands
are reliable. This is the fingerprint region.
Use for comparison with literature spectra.

Wavenumber is cm
-1
=10
4
/()
What kinds of Bonds Absorb in
which Regions?
Bending is easier than stretching-- happens at lower energy
(lower wavenumber)
Bond Order is reflected in ordering-- triple>double>single (energy)
with single bonds easier than double
easier than triple

Heavier atoms move slower than
lighter ones
The k in the frequency equation is in
mDyne/ of displacement
Single bond str 3-6 mD/
Double bond str. 10-12 mD/
Triple Bond 15-18 mD/
Effects of conjugation
Lowers to
1715 cm
-1
Similar, to
1715 cm
-1
Raises to
1770 cm
-1
:

Weakens DB character
Strengthens DB character
(inductive over resonance)
The Vibrations of CO
2
.
The stretching modes are not
independent, and if one CO
group is excited the other begins
to vibrate.
The symmetric and
antisymmetric stretches are
independent, and one can be
excited without affecting the
other: they are normal modes.
The two perpendicular bending
motions are also normal modes.
The Normal Modes of Water
The three normal
modes of H
2
O. The
mode v
2
is
predominantly
bending, and occurs
at lower wavenumber
than the other two.
Introduction to Emission
Luminescence: emission of photons from
electronically excited states of atoms,
molecules, and ions.
Fluorescence: Average lifetime from <10
10
to
10
7
sec from singlet states.
Phosphorescence: Average lifetime from 10
5

to >10
+3
sec from triplet excited states.
Importance of Emission Spectroscopy
Sensitivity to local electrical environment
polarity, hydrophobicity
Track (bio-)chemical reactions
Measure local friction (microviscosity)
Track solvation dynamics
Measure distances using molecular rulers:
fluorescence resonance energy transfer (FRET)
Photophysics: Jablonski Diagram
Kashas rule, Internal Conversion, Intersystem crossing, fluorescence, phosphorescence
Principles
Interaction of photons with molecules
results in promotion of valence electrons
from ground state orbitals to high energy
levels.
The molecules are said to be in excited
state.
Molecules in excited state do not remain
there long but spontaneously relax to more
stable ground state.
The relaxation process is brought about by
collisional energy transfer to solvent or
other molecules in the solution.
Some excited molecules however return to
the ground state by emitting the excess
energy as light.
This process is called fluorescence.
Light Amplification by Stimulated Emission of Radiation
In a laser.
Three key elements in a laser

Pumping process prepares amplifying medium in suitable state
Optical power increases on each pass through amplifying medium
If gain exceeds loss, device will oscillate, generating a coherentoutput
Fate of molecule?
Non-radiative transition: M* + M M + M + heat
Spontaneous emission: M* M + hv (very fast for large
AE)
Stimulated emission (opposite to stimulated absorption)

These factors contribute to linewidth & to lifetime of excited
state.