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CHEM 3510 Fall 2003

Molecular Spectroscopy

Lets consider a system with

'

electrons
nuclei
n
N

This will be described by a wave function ) , ( R r depending on the coordinates of all the
nuclei and all the electrons.
According to Born-Oppenheimer approximation, the wave function can be separated:
) ( ) ; ( ) , ( R R r R r
nu el

Solve for
el
considering a fixed position of the nuclei (at one nuclear
configuration).
Electrons create a potential in which nuclei move. This is called a potential
energy surface for polyatomic and potential energy curve for a diatomic.

1 nucleus
(atom)
2 nuclei
(diatomic)
N (>2) nuclei
(polyatomic)
el
depends on
3n coordinates
el
depends on
3n coordinates
el
depends on
3n coordinates

nu
depends on
6 3 N coordinates
nu
depends on
N 3 coordinates
Linear Nonlinear
3 translational 3 translational 3 translational
2 rotational 2 rotational 3 rotational

1 vibrational 5 3 N vibrational 6 3 N vibrational


CHEM 3510 Fall 2003
Spectroscopy is dealing with the study of the interaction of electromagnetic radiation with atoms
and molecules. Molecular spectroscopy deals with the radiation interacting with molecules.
Electromagnetic radiation is usually divided into different energy regions. The frequency and
energy of the radiation corresponds (is associated) with different types of molecular transitions.

) cm (
~ 1
Region of electromagnetic radiation Molecular Process
0.033-3.3 Microwave Rotation of polyatomic
3.3-330 Far infrared Rotation of small molecules
330-14500 Infrared Vibrations of flexible bonds
14500-50000 Visible and UV Electronic transitions



The energy difference between two energy levels is related to the frequency of radiation
by:
h E E E
l u

Sometimes it is preferred the use of wavenumbers:

1
~

c

CHEM 3510 Fall 2003
Diatomic Molecules
Pure Rotational Spectra
The simplest model for the rotation in a diatomic molecule is the rigid rotator model.
The energy levels predicted by the rigid rotator model:
) 1 (
2
2
+ J J
I
E
J
h

where
2
e
R I and J = 0,1,2,
The degeneracy of J
th
level is 1 2 + J g
J
.
The rotational energy of a molecule (in wavenumbers) is denoted by ) (J F and is called
rotational term.
The energies (in wavenumbers) predicted by the rigid rotator model:
) 1 (
~
) ( + J J B J F where
cI
h
B
2
8
~


The selection rule is 1 t J plus the molecule should have a permanent dipole moment.
Frequency of absorption is given by a transition from J to 1 + J ( 1 + J J ) and is given,
within rigid rotator model, by:
) 1 (
~
2 ) ( ) 1 (
~
+ + J B J F J F v where J = 0,1,2,
Within rigid rotator model, the rotational spectrum of diatomics is predicted to be a series
of lines equally spaced (separated) in microwave region of electromagnetic radiation.
Experimentally the lines are not equally spaced, they get close to
each other as the quantum number increases. The energy levels
are in reality slightly different than predicted by rigid rotator model.
The reason is that centrifugal force causes the bond to stretch slightly.
The energies predicted by the nonrigid rotator model:

2 2
) 1 (
~
) 1 (
~
) ( + + J J D J J B J F
where B
~
is the rotational constant
D
~
is the centrifugal distortion constant
Frequency of absorption is given by a transition from J to 1 + J ( 1 + J J ):

3
) 1 (
~
4 ) 1 (
~
2 ) ( ) 1 (
~
+ + + J D J B J F J F v where J = 0,1,2,
The B
~
and D
~
constants are obtained by fitting this equation to the experimental data.
Rotational transitions also accompany vibrational transitions.
CHEM 3510 Fall 2003
Vibrational Spectra
The simplest model for the vibration in a diatomic molecule is the harmonic oscillator
model.
The energy levels predicted by the harmonic oscillator model:
h v E
v

,
_

+
2
1

where

,
_

k
2
1
is called fundamental frequency,
B A
B A
m m
m m
+

and v = 0,1,2,
The vibrational energy of a molecule (in wavenumbers) is denoted by ) (v G and is called
vibrational term.
The energies (in wavenumbers) predicted by the harmonic oscillator model:

~
2
1
) (
,
_

+ v
hc
E
v G
v
where

k
c 2
1
~
and v = 0,1,2,
The selection rule is 1 t v .
Within harmonic oscillator model, only one line in the spectrum (called the fundamental) in
the IR region should be observed at:

k
2
1
obs
or

k
c 2
1
~
obs

Experimentally it can be observed a series of less intense lines, almost integral multiples of
the fundamental, called overtones due to transitions from 0 v to ,... 3 , 2 v
first overtone: 2 0 v v
second overtone: 3 0 v v
Harmonic-oscillator model does not represent accurately the potential energy far from the
equilibrium distance.
Potential energy ) (R V may be expanded in a Taylor series about
e
R :
( ) ( ) ....
! 3
1
! 2
1
) ( ) (
3
e
3
3
2
e
2
2
e
e e
+

,
_

,
_



R R
dR
V d
R R
dR
V d
R V R V
R R R R

....
24 6 2
4 4 3 3 2
+ + + x x x
k
where
j
j
j
dR
V d

Harmonicoscillator approximation (model) consists in keeping
only quadratic term.
CHEM 3510 Fall 2003
Once the anharmonic terms (contributions) are included, the vibrational term becomes:
( ) ( ) ....
~ ~ ~
) (
2
2
1
e e
2
1
e
+ + + v x v v G where ... 2 , 1 , 0 v
where
e
x is the anharmonicity constant
anharmonic corrections are much smaller than the harmonic term 1
e
<< x
The energy levels are not evenly spaced in anharmonic oscillator model, and the energy
difference gets smaller as quantum number v increases.
Selection rule: ... 3 , 2 , 1 t t t v
) 1 (
~ ~ ~
) 0 ( ) (
~
e e e obs
+ v v x v G v G where ... 3 , 2 , 1 v
Considering anharmonic terms improve agreement with experiment.
Vibration-Rotation Spectra
Rotational transitions also accompany vibrational transitions.
The energies predicted by the rigid rotator- harmonic oscillator approximation:
( ) ) 1 (
~
~
) ( ) (
~
2
1
,
+ + + + J J B v J F v G E
J v

The absorption in IR region of spectrum

'

t
+
1
1
J
v

1 + J ( ) 1
~
2
~
~ ~
) 1 (
~
, 1 , 1 obs
+ + +
+ +
J B E E J
J v J v

1 J ( ) J B J
~
2
~
1
~
obs


1 + J R branch
1 J P branch
( 0 J Q branch)


The spectrum is predicted to be a series of lines equally spaced (with one line missing) in
the IR region of electromagnetic radiation.
Labeling the lines in vibrationrotation spectrum is based on the branch and on the value of
J in the lower state:

'

....
) 1 (
) 0 (
) ( R
R
J R and

'

....
) 2 (
) 1 (
) ( P
P
J P
CHEM 3510 Fall 2003
Experimentally the lines are not equally spaced: on the P branch they get farther apart from
each other as the quantum number increases and on the R branch they get closer to each
other as the quantum number increases. Vibration-rotation interaction explains the
unequal spacing between lines in vibration-rotation spectrum.
Because
e
R vary (increases) slightly with v, consider that rotational constant B is
dependent on the vibrational state v:
( ) ) 1 (
~
~
~
2
1
,
+ + + J J B v E
v J v

The dependence of B
~
on v is called vibration-rotation interaction.
The frequencies of the lines in the vibration-rotation spectrum considering the
vibration-rotation interaction:

2
0 1 0 1 1 , 0 1 , 1
)
~ ~
( )
~ ~
3 (
~
2
~ ~
J B B J B B B E E
J J R
+ + +
+


2
0 1 0 1 , 0 1 , 1
)
~ ~
( )
~ ~
(
~ ~
J B B J B B E E
J J P
+


The dependence of
v
B
~
on v is given by:
( )
2
1
e e
~
~ ~
+ v B B
v

One can see that
1
~
B <
0
~
B : the spacing between P branch lines increase with J
the spacing between R branch lines decrease with J
The energies predicted by the nonrigid rotator-anharmonic oscillator model including the
vibration-rotation interaction:
( ) ( ) ( ) ) 1 (
~
) 1 (
~
) 1 (
~
~ ~ ~
~
2
1
e
2 2
e
2
2
1
e e
2
1
e ,
+ + + + + + + J J v J J D J J B v x v E
J v

The absorption in IR region of spectrum

'

t
t t t
1
3 , 2 , 1
J
v

Neglecting the
2 2
) 1 (
~
+ J J D term:

2
e e e e e 0 , 0 1 , 1 obs
~
)
~
4
~
2 ( )
~
3
~
2 (
~
~ ~
) 1 (
~
J J B B E E J
J J
+ + +
+


2
e e e 0 , 0 1 , 1 obs
~
)
~
2
~
2 (
~
~ ~
) 1 (
~
J J B E E J
J J



where
e e e 0
~ ~
2
~ ~
x
Introducing a new quantity m where 1 + J m for the R branch and J m for
the P branch.

2
e e e 0
~
)
~
2
~
2 (
~
) (
~
m m B m +
Considering the
2 2
) 1 (
~
+ J J D term:

3 2
e e e 0
4
~
)
~
2
~
2 (
~
) (
~
Dm m m B m +
CHEM 3510 Fall 2003
Electronic spectra
Molecules can undergo transitions between electronic
levels and the electronic transitions are accompanied
by both rotational and vibrational transitions.
According to BO approximation, the electronic
energy is independent of the vibrational-rotational
energy.
Using anharmonic oscillator- nonrigid rotator
approximation but excluding translational energy, the
total energy is:

( ) ( ) ( ) ( )
2 2
2
2
1
e e
2
1
e el
el total
1
~
1
~
~ ~ ~ ~
) ( ) (
~
+ + + + + +
+ +
J J D J J B v x v
J F v G E


where
el
~
is the energy (in wavenumbers) at the minimum of the electronic
potential energy curve.
Ignore the rotational levels from the discussion (and formula) because their energies are
much smaller.
All vibrational transitions in electronic spectra (vibronic transitions) are allowed.
Usually the transitions originate from the ground state electronic state with 0 v
vibrational state.
( ) ( ) ( ) 1
~ ~ ~ ~ ~ ~ ~ ~ ~
~
~
e e e e
4
1
e
2
1
e e
4
1
e
2
1
e obs
+ + + v v x v x x T
e

where
e
~
T is the difference in minimum of the two
electronic potential energy curves, notation is
used for upper energy state, and notation is used
for lower energy state.
Look at a case of two electronic states:
Use Morse curves to represent these curves:
[ ]
2
) (
e
e
1 ) (
R R
e D R V




Define dissociation energies:

e
D is the difference between the minimum of the
potential energy curve and the dissociated atoms.

0
D is the difference between the ground
vibrational level and the dissociated atoms.
CHEM 3510 Fall 2003
For a harmonic oscillator: h D D
2
1
0 e
+
For a anharmonic oscillator: ) (
e e
2
1
e
2
1
0 e
x h D D +
Define 0 0 vibronic transition as the transition between the zero-point energies of upper
and lower electronic states.
( ) ( )
e e
4
1
e
2
1
e e
4
1
e
2
1
0 , 0
~ ~ ~ ~ ~ ~
~
~
+ x x T
e

) 1 (
~ ~ ~ ~ ~
e e e 0 , 0 obs
+ + v v x v where ... 2 , 1 , 0 v
The spectrum look like a bunch of lines called v
progression. It can be used to get information about
vibrational parameters of excited electronic states.



Franck-Condon Principle
It says that the electronic transitions are vertical. Because the motion of the
electrons is almost instantaneous relative to the motion of nuclei, when an
electron makes a transition from one electronic state to another, the nuclei do
not move appreciably during the transition.
The Franck-Condon principle allows estimation of relative intensity of vibronic
transitions. The intensity is proportional to the overlap between the wave
function in the upper and lower vibronic states.
Sometimes if the excited state potential curve is displaced to sufficient larger
internuclear distance than at the ground state potential curve, then the
absorption spectra may not contain a line corresponding to
0 , 0
~
.
A detailed analysis of the intensities of such vibronic transitions yields more
information about the potential energy curves (that cannot be found in
vibrational or rotational spectra).
CHEM 3510 Fall 2003
Polyatomic molecules
Rotational Spectra
A rigid body is characterized by its principal moments of inertia defined as follows (the
moments of inertia are defined about 3 arbitrary axes):
[ ]

+
N
j
j j j xx
z z y y m I
1
2
cm
2
cm
) ( ) ( ; [ ]

+
N
j
j j j yy
z z x x m I
1
2
cm
2
cm
) ( ) (
[ ]

+
N
j
j j j zz
y y x x m I
1
2
cm
2
cm
) ( ) (
where cm stands for the center of mass of the molecule (body),
j j j
z y x , , are
the coordinates of atom j, and N is the number of atoms in the molecule.
There will be other terms of form [ ]


M
j
j j j xy
y y x x m I
1
cm cm
) )( (
Choose 3 axis (X, Y, Z) called principal axes so the
xy
I ,
xz
I ,
yz
I terms vanish. In that
case,
xx
I ,
yy
I , and
zz
I are called principal moments of inertia.
Principal axes are easy to find for molecules with some degree of symmetry.
For planar molecule: one principal axis is perpendicular per molecular plane
For Cl CH
3
: one principal axis is the
3
C axis.
We do not need to know how to find those axes (they are tabulated) but we will work with
the rotational constants (in
1
cm

):
A
2
8
~
cI
h
A

,
B
2
8
~
cI
h
B

, and
C
2
8
~
cI
h
C


Because
C B A
I I I C B A
~ ~ ~

Based on the relative magnitudes of the three principal
moments of inertia of a rigid body, they can be divided in:
linear rotor or top (one moment of inertia is zero).
Examples:
2
CO ,
2 2
H C
spherical rotor or top (all three principal moments of
inertia are equal). Examples:
4
CH ,
6
SF
symmetric rotor or top (two principal moments of
inertia are equal). (Molecules with
n
C ( 3 > n ) are at
least a symmetric top.) Examples:
3
NH ,
6 6
H C
asymmetric rotor or top (none of the principal
moments of inertia are equal). Examples: O H
2

CHEM 3510 Fall 2003
Spherical top
The problem can be solved exactly and the energy levels are given by:
) 1 (
~
) ( + J J B J F where ,... 2 , 1 , 0 J
The degeneracy of J level is:
2
) 1 ( 2 + J g
J

Symmetric top
oblate symmetric top (unique moment of inertia is larger than the other two):

zz yy xx
I I I < (
xx
I I
A
,
yy
I I
B
,
zz
I I
C
)
Examples:
3
BCl ,
6 6
H C
Energy levels are given by:
2
)
~ ~
( ) 1 (
~
) , ( K B C J J B K J F + +
where degeneracy is 1 2 + J g
JK
, ,... 2 , 1 , 0 J , ,... 2 , 1 , 0 t t K
The quantum number J is a measure of total rotational angular
momentum and K is a measure of the component of rotational
angular momentum along the unique axis of symmetry.
prolate symmetric top (unique moment of inertia is smaller than the other two):

zz yy xx
I I I > (
xx
I I
C
,
yy
I I
B
,
zz
I I
A
)
Examples: I CH
3

Energy levels are given by:
2
)
~ ~
( ) 1 (
~
) , ( K B A J J B K J F + +
where degeneracy is 1 2 + J g
JK
, ,... 2 , 1 , 0 J , ,... 2 , 1 , 0 t t K
Selection rules:

'

t
t
0 for 0 and 1
0 for 0 and 1 , 0
K K J
K K J

If 1 + J (absorption) and 0 K ) 1 (
~
2
~
+ J B
Polyatomic molecules are less rigid than diatomics so centrifugal distortion
effects are more pronounced. One needs to apply nonrigid rotator model. For
symmetric top:

3 2
) 1 (
~
4 ) 1 (
~
2 ) 1 (
~
2
~
+ + + J D J K D J B
J JK

this predicts any rotational transition will consist of a series of
lines depending on the value of K.

Asymmetric top
complicated formulas
CHEM 3510 Fall 2003
Vibrational spectra
A N-atom molecule has 3N degrees of freedom.
Linear Nonlinear
Translational 3 3
Rotational 2 3
Vibrational 3N5 3N6
Total 3N 3N
Examples: acetylene (
2 2
H C ): The number of vibrational degree of freedom is
water ( O H
2
): The number of vibrational degree of freedom is
The displacements (
vib
,... ,
2 1 N
q q q ) from equilibrium position can be used to do a
multidimensional Taylor expansion:



+
vib vib
vib
1 1
2 1
...
2
1
) 0 ,..., 0 , 0 ( ) ,..., , (
N
i
N
j
j i ij N
q q f V q q q V V
where
j i
ij
q q
V
f

2

A new set of coordinates { } Qj can be found such that:


vib
1
2
2
1
N
j
j j
Q F V
where Qj are called normal modes or normal coordinates.
Using these normal modes, the vibrational Hamiltonian operator becomes a sum of
independent terms so the total wave function (describing the nuclear motion) is a product
of individual wave functions and the energy is a sum of individual energies:



,
_

+
vib vib
1
2
2
2 2
1
, vib vib
2
1
2

N
j
j j
j
j
N
j
j
Q F
dQ
d
H H

h

) ( )... ( ) ( ) ,..., , (
vib vib vib
vib, 2 vib,2 1 vib,1 2 1 vib N N N
Q Q Q Q Q Q
( )

+
vib
1
2
1
vib
N
j
j j
v h E where each ... 2 , 1 , 0
j
v
The vibrational motion of a polyatomic molecule appears as
vib
N independent
(harmonic or anharmonic) oscillators. Without degeneracies there will be
vib
N
characteristic fundamental frequencies
j
.
CHEM 3510 Fall 2003
A normal mode is a synchronous motion of atoms or group of atoms that does not change
the center of mass of the molecule. Being independent, one normal mode may be excited
without leading to the excitation of any other mode.
Examples:
2
CO O H
2


The activity of normal modes: Which normal modes are active? (Which normal mode
appears in the vibrational absorption spectra?)
The vibrations (normal modes) are infrared active only if the dipole moment of
the molecule changes when the atoms are displaced relative to one another.
All the water normal modes and two of the
2
CO are IR active.
One normal mode of
2
CO (symmetric stretch) is IR inactive.
Homonuclear diatomic are IR inactive.
Heteronuclear diatomic are IR active.
The case of
2
CO :
asymmetric stretch: dipole moment oscillates parallel to molecular axis Such
a band is called parallel band.
Selection rules: 1 v
1 t J P and R branches only
bending modes: dipole moment oscillates perpendicular to molecular axis
Such a band is called a perpendicular band.
Selection rules: 1 v
1 , 0 t J P, Q, and R branches appear
CHEM 3510 Fall 2003
Each normal mode in polyatomic molecules belongs to an irreducible representation. This
is a result of the fact that the vibrational properties of a molecule change under any
symmetry operation. Each normal mode (coordinate) transforms as an irreducible
representation of the point group that molecule belongs to.
Example: O H
2

Symmetric stretch:
ss
Q

ss ss

Q Q E ;
ss ss 2

Q Q C ;
ss ss
Q Q
v
;
ss ss
Q Q
v

Asymmetric stretch:
as
Q

as as

Q Q E ;
as as 2

Q Q C ;
as as
Q Q
v
;
as as
Q Q
v

Bending mode
A more general way to determine what irreducible representations the normal modes
belong to:
A) Determine the reducible representation for the nuclear motion
Put the 3 coordinate axes on each atom
Do each symmetry operation, write the result in a form of a matrix of
transformation, and determine its character.



E

C
v

v


N 3

Simpler, count +1 for every coordinate that does not change place and sign, 1
for every coordinate that does not change place but changes sign, and 0 for
every coordinate that changes place.
More general, the entries for the various rotation axes can be deduced from the
rotation matrix. For a rotation with degrees (
/ 360
C ), the rotation matrix is
given by

,
_

,
_

,
_

z
y
x
z
y
x
1 0 0
0 cos sin
0 sin cos


and for the improper rotation with
degrees (
/ 360
S ), the rotation matrix is

,
_

,
_

,
_

z
y
x
z
y
x
1 0 0
0 cos sin
0 sin cos


.
O
H H
O
H H
O
H H
CHEM 3510 Fall 2003
Table with contribution that each unmoved atom makes to the character of the
3N-dimensional representation obtained by operating on arbitrary
(3-dimensional) vectors attached to each of the N atoms in the molecule:
R

C
i


2
3 3

C C
3
4 4

C C
5
6 6

C C
2

S
2
3 3

S S
3
4 4

S S
5
6 6
,

S S
Contribution
to )

(R
3 1 3 1 0 1 2 3 2 1 0
B) Reduce
N 3
to irreducible representations
v 2
C
E

C
v

v


1
A
1 1 1 1 z
2
x ,
2
y ,
2
z
2
A
1 1 1 1 z
R xy
1
B
1 1 1 1
x,
y
R
xz
2
B
1 1 1 1
y,
x
R yz
N 3

9 1 1 3
[ ] 3 1 3 1 1 1 1 1 9
4
1
1
+ + +
A
a
Similarly: 1
2

A
a ; 2
1

B
a ; 3
2

B
a

2 1 2 1 3
3 2 3 B B A A
N
+ + +
C) From
N 3
, subtract the irreducible representations of the 3 translational degrees of
freedom denoted
x
T ,
y
T , and
z
T (same as x, y, and z) and the irreducible
representations of the 2 or 3 rotational degrees of freedom denoted
x
R ,
y
R , and
z
R .

2 1 vib
2 B A +

Selection Rules for Transitions Between Two States
The probability of transit ion between 2 states (determined from perturbation theory) is
proportional to the transition dipole moment:
( )

d
z z 1
*
2
12

(this is the z component of the transition dipole moment)
If the transition dipole moment is zero the transition is not observed (or not allowed or
forbidden).
If the transition dipole moment is not zero the transition is observed (or allowed).
If dipole moment is zero then transition dipole moment is zero.
CHEM 3510 Fall 2003
Selection rules for rigid rotator can be deduced from this condition, and they are:

'


t
) 0 or ( 0
1
K M
J

Selection rules for harmonic oscillator can be deduced from this condition, and they are:

'

,
_

t
0
1
0
dq
d
v


Determining the IR/Raman activity of normal mode vibrations using group theory
IR activity
Transition dipole moment for a 1 0 v v transition:
( ) ( )
vib vib vib
.... ,..., , ,..., ,
2 1 2 1 1 2 1 0 1 0 N N
z
y
x
N
dQ dQ dQ Q Q Q Q Q Q I

'


This integral is (should be) invariant to symmetry operations.

1 0 1 0
)

( )

( )

, , 1

I R R R I R
j z y x
Q A



1 )

( )

( )

(
, , 1
R R R
j z y x
Q A


for the transition to be allowed.
The product should transform as the totally symmetric representation
(
1
A ,
g
A , etc)
Example for O H
2
(
v 2
C group)
Initial state Dipole moment Final State
(normal mode)
Result
1
A
x
1
B
y
2
B
z
1
A
1
A
x
y
z
1
A
x
1
B
y
2
B
z
1
A
2
B
x
y
z
All normal modes are IR active
CHEM 3510 Fall 2003
Raman activity
Similar to IR activity but instead of the dipole moment in the integral one uses
polarizability that appear as a product of two coordinates (
2
x ,
2
y , etc)
Transition is Raman active if )

( )

( )

(
1
R R R
j
a A


is equal to 1.
Example for O H
2
(
v 2
C group)
Initial state Dipole moment Final State
(normal mode)
Result
1
A
2
x
1
A
2
y
1
A
2
z
1
A
xy
2
A
xz
1
B
yz
2
B
1
A
2
x
2
y
2
z
xy
xz
yz
1
A
2
x
1
A
2
y
1
A
2
z
1
A
xy
2
A
xz
1
B
yz
2
B
2
B
2
x
2
y
2
z
xy
xz
yz
All normal modes are IR active
Mutual Exclusion Rule: For molecules with a center of inversion, the normal modes
are active in either IR or Raman but not in both IR and Raman.
Examples:
2
CO ,
2 2 2
Cl H C trans


CHEM 3510 Fall 2003
Determining the IR/Raman activity of normal mode vibrations of CCl
4
using group theory
d
T
E


8
3

C 3
2

C 6
4

S
6
d


1
A
1 1 1 1 1
2
x + +
2
y
2
z
2
A
1 1 1 1 1
E 2 1 2 0 0
( , )
2 2 2
2 y x z
2 2
y x
1
T
3 0 1 1 1
( , ,
x
R
y
R
z
R )

2
T
3 0 1 1 1 (x, y, z)
( xy , xz , ) yz
N 3

15 0 1 1 3
C
Cl Cl
Cl Cl

A) Determine the reducible representation for nuclear motion
N 3

B) Reduce to irreducible representations
N 3
[ ] 1 1 3 6 1 ) 1 ( 6 1 ) 1 ( 3 1 0 8 1 15
24
1
1
= + + + + =
A
a
[ ] 0 ) 1 ( 3 6 ) 1 ( ) 1 ( 6 1 ) 1 ( 3 1 0 8 1 15
24
1
2
= + + + + =
A
a
[ ] 1 0 3 6 0 ) 1 ( 6 2 ) 1 ( 3 ) 1 ( 0 8 2 15
24
1
= + + + + =
E
a
[ ] 1 ) 1 ( 3 6 1 ) 1 ( 6 ) 1 ( ) 1 ( 3 0 0 8 3 15
24
1
1
= + + + + =
T
a
[ ] 3 1 3 6 ) 1 ( ) 1 ( 6 ) 1 ( ) 1 ( 3 1 0 8 3 15
24
1
2
= + + + + =
T
a

2 1 1 3
3T T E A
N
+ + + =
C) Determine the vibrational contribution to
N 3

; ;
2 trans
T =
1 rot
T =
2 1 vib
2T E A + + =
4 different frequencies (three of them are degenerate: one doubly degenerate
and two triply degenerate)
D1) Determine IR activity D2) Determine Raman activity
1
A not active active
1
A
E not active E active
2
T active active
2
T
E) Only totally symmetric vibrations give rise to polarized lines (in which the incident
polarization is preserved).
C
Cl Cl
Cl Cl

C
Cl Cl
Cl Cl

C
Cl Cl
Cl Cl

C
Cl Cl
Cl Cl


CHEM 3510 Fall 2003
Deexcitation processes from electronically excited states
A molecule does not remain in an excited state; it decays back to the ground state.
Exemplify the pathways from which electronically excited (diatomic) molecules decay to
their ground state.


Consider:
0
S is the singlet ground state

1
S is the first excited singlet state

1
T is the first excited triplet state

Assume that:
1
T is lower in energy than
1
S
) ( ) ( ) (
1 e 1 e 0 e
T R S R S R < <


There can be two types of transitions:
radiative (transition between energy levels that involve absorption or emission
of radiative transitions)
nonradiative (transition between energy levels without absorption or emission of
radiation)
The activation/deactivation processes and their time scales:
1.) Absorption from
0
S to
1
S
s 10 ~
9
2.) Fluorescence (a radiative transition from
1
S to
0
S )
s 10 10 ~
12 7
3.) Internal Conversion (nonradiative transition from
1
S to
0
S )
s 10 10 ~
16 6
4.) Intersystem Crossing (nonradiative transition from
1
S to
1
T )
(slower)
s 10 10 ~
7 5
5.) Phosphorescence (a radiative transition from
1
T to
0
S )
s 10 10 ~
8 3
6.) Intersystem Crossing (a nonradiative transition from
1
T to
0
S )
s 10 ~
14
7.) Vibrational Relaxation (nonradiative process) due to collisions
with other molecules (very fast)

CHEM 3510 Fall 2003
Absorption and fluorescence spectroscopy
Consider a diatomic molecule with ) ( ) (
1 e 0 e
S R S R
Consider the vibrational levels of: ground electronic state ( ' ' v )
excited electronic state ( ' v )
Absorption spectra:
It is a series of lines reflecting transitions from 0 v of the ground electronic
state to ,... 2 , 1 , 0 ' v of the excited electronic state.
The spacing between lines is determined by energy gap between vibrational
states of excited states.
Fluorescence spectra:
It is a series of lines reflecting transitions from 0 ' v of the excited electronic
state to ,... 2 , 1 , 0 v of the ground state electronic state.
The spacing between lines is determined by energy gap between vibrational
states of ground state.
The transition from 0 ' v to 0 v , called 00 transition, appear in both absorption and
fluorescence spectra.
The relative intensities of the absorption and emission lines are determined by Frank-
Condon principle.
Fluorescence spectra appear at higher and lower than the absorption spectra


Phosphorescence occurs at lower energy (frequency) than fluorescence.
CHEM 3510 Fall 2003
Lasers (Light Amplification by Stimulated Emission of Radiation)
Lasers are devices that exploit the amplification of light though stimulated emission.
Consider 2 energy levels (Example; two electronic levels in an atom so no vibrational and
rotational contributions) and assume no degeneracy.

2 1
, N N are the number of atoms in each state

2 1 total
N N N +

2 1
,E E are the ground and excited state energies
Assume no degeneracies (for simplicity)
Assume kT E E >>
1 2
(average energy at temperature T) so all molecules are in state 1.
Expose the sample to electromagnetic radiation:
12 1 2
h E E
Define: radiant energy density (radiant energy per unit volume: units of
3
m
J
)
spectral radiant energy density

d
d
( radiant energy density per unit
frequency: units of
3
m
Js
)
The rate of excitation from ground electronic state to excited electronic state:

dt
t dN
t N B
dt
t dN ) (
) ( ) (
) (
2
1 12 12
1

(if no emission)
where
12
B is called Einstein coefficient
Einstein proposed 2 pathways to treat relaxation back to ground state:
spontaneous emission
) (
) (
2 21
2
t N A
dt
t dN
(if no other process)
where
12
A is Einstein coefficient and
R
21
1

A
is fluorescence
lifetime (radiative lifetime)
stimulated emission (proportional to ) (
12

; amplify light intensity)


) ( ) (
) (
2 12 21
2
t N B
dt
t dN


where
21
B is Einstein coefficient
If no other processes then:
) ( ) ( ) ( ) ( ) (
) ( ) (
2 12 21 2 21 1 12 12
2 1
t N B t N A t N B
dt
t dN
dt
t dN



CHEM 3510 Fall 2003
At equilibrium:
0
) ( ) (
2 1

dt
t dN
dt
t dN

21 12
1
2
21
12
) (
B B
N
N
A
v
v

,
_


But
T k h
e
N
N
B 12
/
1
2
and
1
8
) (
B 12
/
3
12
3
12

T k h
e c
h


(blackbody radiation)

21 12
B B and
21
3
3
12
21
8
B
c
h
A


Einsteins coefficients are related.
Consider the case of only 2 levels:
One can achieve stimulated emission if the stimulated emission is greater than
the rate of absorption.

1 12 12 2 12 21
) ( ) ( N B N B

>

1 2
N N > The population in the excited state is greater than
in the lower state. This is called population inversion, and it is
a non-equilibrium situation.
It can be shown that:

2
1
) ( 2
) (
12
12
2 1
2
total
) ( 2
<
+

B A
B
N N
N
N
N
t
because 0 > A .

The population inversion cannot occur in a two level system.


Consider the case of 3 levels:
A light beam
31
h called the pump source is used to create
excited-state populations.
31
h is the pump light.
The rates of spontaneous emission from state 3 to state 2 and 1
can be different ) , (
21 31
A A
The total number of molecules ) ( ) ( ) (
3 2 1 total
t N t N t N N + +
At equilibrium:
) (
) (
32 32 32
32 32 21
2
3

B A
B A
N
N
+
+

A population inversion is obtained 1
2
3
>
N
N

if
32 21
A A > .
Such a system is called a gain medium.
CHEM 3510 Fall 2003
Laser Components
Gain medium that amplifies light of desired wavelength
solid-state material
liquid solution
gas mixture
Pumping source that excites the gain medium
optical excitations (lasers convert a max of 50-70% of incident light)
electrical excitations (more common for gas lasers)
Mirrors that direct the light beam back and forth through gain medium
One is 100 % reflective wand the other is < 100 % reflective.
They create a laser cavity (resonator) without which the laser would not work.

Lasers

'

pulsed
continuous

Another important property of the laser light is that the light
is monocromatic (single color-wavelength) and that the light
waves are all in phase. This property is called coherence.
This is due to the fact that stimulated emission has the
incident light wave and stimulated light wave have the same
phase.
Ruby laser
It was the first used laser.
Ruby is a crystal of
3 2
O Al with some
+ 3
Cr impurities.
Electronic energy levels of
+ 3
Cr in
3 2
O Al are
suitable for achieving a population inversion.
Pulsed laser that works at 694.3 nm.
CHEM 3510 Fall 2003
Yttrium-aluminum garnet (YAG) laser

15 5 3
O Al Y (YAG) impurities with
+ 3
Nd which is the active ion
Can be both pulsed and continuous lasers; work at 1064.1 nm.
Other lasers based on Nd can have similar wavelength:
1054.3 nm for
y x
F Li Y
3
(YLF)
1059 nm for
+ 3
Nd in glass

2 2
CO N laser (gas lasers)
Population inversion can be achieved is some vibrational levels of
2
CO in
ground electronic state (closer to each other than
2
N )
Continuous laser that can become tunable lasers through the rotational levels.
HeNe laser (gas-phase laser)
Contains a gas mixture in a glass cell
Typical gas pressures 1.0 torr for He and 0.1 torr for Ne
Continuous laser that can work at 4 different wavelengths: 3391.3, 1152.3,
632.8, and 543.5 nm
Excitation occurs through electrical discharge that produces excited He atoms.
This is followed by a nonradiative energy transfer through collisions from He to
Ne. The lifetimes of these excited states of Ne are such that population
inversion can be achieved. Several transitions are used to generate laser light.
(There are few Ne transitions that have been observed to lase.)
Chemical laser
It is based on the H HF H F
*
2
+ + reaction.
F is formed by electric discharge in H SF
6
+ reaction.
The HF is formed in a vibrational excited state (so population inversion is
achieved). Two transitions can lase.
The use of lasers:
In everyday life, medicine, military (targeting), chemistry
In spectroscopy: the use of high-resolution lasers can resolve absorption lines
that cannot be distinguished by conventional spectrometers
In photochemistry (the field of light- initiated reactions)
For studying chemical reactions with high spectral and time resolution (order of
15
10

seconds = femtoseconds)

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