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Molecular Vibrations

So, that is the situation for the simple harmonic oscillator.


Question is, how does this treatment get extended to larger
molecular systems? Well lets see. We will start by consider a
linear molecule, CO2. While our first attempt will be from a
classical physics standpoint, the quantum extension will be
obvious.
M M
k m k

x1 x2 x3
Molecular Vibrations
From a classical physics standpoint, M
each mass is represented by a k m k M
different coordinate (here we are
restricting our attention to the x-axis
only) and we can write an expression
x1 x2 x3
for each mass in terms of Newtons
Second Law, viz

M&x&1 = − k ( x1 − x 2 )
m&x& 2 = − k ( x 2 − x1 ) − k ( x 2 − x 3 )
M&x&3 = − k ( x 3 − x 2 )
Molecular Vibrations
From a classical physics standpoint, M m M
k k
each mass is represented by a
different coordinate (here we are
restricting our attention to the x-axis
only) and we can write an expression x1 x2 x3
for each mass in terms of Newton’s
Second Law, viz

M&x&1 = − k ( x1 − x 2 )
m&x& 2 = − k ( x 2 − x1 ) − k ( x 2 − x 3 )
M&x&3 = − k ( x 3 − x 2 )
Molecular Vibrations
The equations can be rewritten as

k
&x&1 = − ( x1 − x 2 )
M
k k
&x& 2 = − ( x 2 − x1 ) − ( x 2 − x 3 )
m m
k
&x&3 = − ( x 3 − x 2 )
M

Given that the system of masses is vibrating, we focus our


attention on the cases where all masses are vibrating at a common
frequency. Such frequencies are referred to as normal modes.
Molecular Vibrations
We can assume the vibrational changes in position x, in terms of
iωt
the normal modes, ω, will be of the form x i = x i , 0e . Inserting
this function into our earlier expression leads to

k
ω x1 = ( x1 − x 2 )
2

M
k k
ω x 2 = ( x 2 − x1 ) + ( x 2 − x 3 )
2

m m
k
ω x3 = (x 3 − x 2 )
2

where the common factor eiωt has been divided out.


Molecular Vibrations
These three expressions represent a system of equations that can
be cast in matrix form

⎛ k −
k
0 ⎟⎞

⎜ M M ⎟⎛⎜ x1 ⎞⎟ ⎛ x1 ⎞
⎜ ⎟
⎜ − k 2k −
k⎟
⎜ x2 ⎟ = ω ⎜ x2 ⎟
2

⎜ m m m ⎟⎜ ⎟ ⎜x ⎟
⎜ k x
k ⎟⎝ 3 ⎠ ⎝ 3⎠
⎜ 0 − ⎟
⎝ M M ⎠
Molecular Vibrations
We can cast this expression in the form of a secular determinant,
viz

k k
− ω2 − 0
M M
k 2k k
− − ω2 − =0
m m m
k k
0 − − ω2
M M
Molecular Vibrations
Which can be factored to give

⎛ k 2 ⎞⎛ 2 2k k ⎞
ω ⎜ − ω ⎟⎜ ω − − ⎟ = 0
2

⎝M ⎠⎝ m M⎠
giving rise to the eigenvalues
k k 2k
ω = 0, ω = , ω = +
2 2 2

M M m
To solve for x1, x2 and x3 we simply need to insert these
eigenvalues back into the system of equations.
Molecular Vibrations
For example, ω2 = 0 leads to
x1 − x2 =0
− x1 + 2 x 2 − x3 =0
− x2 + x3 =0
Which in turn yields, x1 = x2 = x3. Thus ω2 = 0 describes pure
translation of the molecule. You should convince yourself that
ω2= k/M leads to x1= -x3 and x2 = 0 or the symmetric stretch of
CO2. Finally, for ω2= k/M + 2k/m, we find that x1 = x3 and
x2 = -2Mx1/m. This last eigenvalue thus corresponds to the
asymmetric stretch of CO2. Those of you that have been through
the undergrad Pchem course here recognize that CO2 also
possesses two degenerate bending modes. However, we restricted
ourselves here to just the x-axis.
Molecular Vibrations
Graphically, we would say that the normal modes for carbon
dioxide are
Molecular Vibrations
You can imagine that for more complicated (larger) molecules,
performing an analysis, such as we just did, could get quite
involved. In many cases, we can take advantage of symmetry in
the molecule to simply this analysis. The use of symmetry
involves a branch of mathematics known as group theory.
Group Theory
First of all, what is a group?
Mathematically, a group is nothing more than a collection of
elements that are interrelated by a certain set of rules.
What are these rules?
1. The product of any two elements and the square of any
element must also be members of the group.
Note however that will AB = C, BA will not necessarily
be C. In other words, the elements may not commute.
2. At least one element in the group must commute with all
other elements. This element is generally known as the
identity element and, by convention, is given the label E.
Symbolically, AE = EA = A.
Group Theory
3. The associative law of multiplication must hold, i.e.,
A(BC)=(AB)C.
4. Every element must have a reciprocal, which is also a
member of the group. By definition, A is the reciprocal of B
if AB = E.

Groups may be either finite or infinite. For finite groups, the


number of elements is referred to as the order of the group.
Often, the order is represented by the symbol h. Now, if we
have a complete and non-redundant list of elements for a
finite group, and we know what all of the products are, then
the group is said to be completely and uniquely defined.
Group Theory
A convenient way to present all of the information about the
group is through the use of a group multiplication table. For
example, lets say that we have a group with the elements A, B
and E. We can construct a multiplication table as shown below

E A B
E E A B
A A
B B
Group Theory
To complete the table, we will utilize the rearrangement
theorem which states that “each row and each column in the
group multiplication table lists each of the group elements once
and only once. In other words, having two identical rows or
two identical columns is not allowed.
E A B Thus, to complete the
E E A B table, either AA=B or
AA=E. Assuming the
A A B E
former, we would write
B B E B
Group Theory
In any group, it is of course possible to identify subgroups. For
example, the identity element is a group of order 1. If the
group can be divided into smaller sets, these sets are called
classes. In group theory, we say that a complete set of
elements which are conjugate to one another represents a class
of the group. Now what does conjugate to one another mean?

We say that two elements are conjugate to one another if they


are related by a similarity transformation
A = X −1BX
Here we say that B is the similarity transformation of A by X.
Group Theory
How is all of this stuff related to molecular spectroscopy?

Molecules have symmetry. Some molecules have more or a


higher level of symmetry than others, but we can identify
symmetry operations for any molecule. One could argue that
group theory, from our perspective, is nothing more than a
means to apply some formal mathematical criteria to the
concept of molecular symmetry. In other words, we are
interested in identifying the set of symmetry operations for a
particular molecule as a mathematical group. We will see that
such an identification leads to a powerful analysis capability.
Group Theory
To begin with, lets work out the group theory representation for
water.

1 2

What are the symmetry operations for this molecule? E,


C2v, σv, σv’.
Group Theory
Now each of these symmetry operations can be mathematically
described by a matrix, viz
⎛ x'⎞ ⎛ x ⎞ ⎡1 0 0 ⎤ ⎛ x ⎞
⎜ ⎟ ⎜ ⎟ ⎢ ⎥ ⎜ ⎟
3 ⎜ y ' ⎟ = E ⎜ y ⎟ = ⎢0 1 0 ⎥ ⎜ y ⎟
⎜ z' ⎟ ⎜ z ⎟ ⎢0 0 1 ⎥ ⎜ z ⎟
⎝ ⎠ ⎝ ⎠ ⎣ ⎦⎝ ⎠
1 2
⎛ x'⎞ ⎛ x ⎞ ⎡ − 1 0 0⎤ ⎛ x ⎞
⎜ ⎟ ⎜ ⎟ ⎢ ⎥ ⎜ ⎟
⎜ y' ⎟ = C 2 v ⎜ y ⎟ = ⎢ 0 − 1 0⎥ ⎜ y ⎟
⎜ z' ⎟ ⎜ z ⎟ ⎢ 0 0 1⎥⎜ z ⎟
⎝ ⎠ ⎝ ⎠ ⎣ ⎦⎝ ⎠
Group Theory

⎛ x'⎞ ⎛ x ⎞ ⎡1 0 0 ⎤ ⎛ x ⎞
⎜ ⎟ ⎜ ⎟ ⎢ ⎥ ⎜ ⎟
⎜ y ' ⎟ = σ v ⎜ y ⎟ = ⎢0 − 1 0 ⎥ ⎜ y ⎟
⎜ z' ⎟ ⎜ z ⎟ ⎢0 0 1 ⎥ ⎜ z ⎟
3 ⎝ ⎠ ⎝ ⎠ ⎣ ⎦⎝ ⎠

1 2
⎛ x'⎞ ⎛ x ⎞ ⎡ − 1 0 0⎤ ⎛ x ⎞
⎜ ⎟ ⎜ ⎟ ⎢ ⎥ ⎜ ⎟
⎜ y' ⎟ = σ v ⎜ y ⎟ = ⎢ 0 1 0⎥ ⎜ y ⎟
'

⎜ z' ⎟ ⎜ z ⎟ ⎢ 0 0 1⎥⎜ z ⎟
⎝ ⎠ ⎝ ⎠ ⎣ ⎦⎝ ⎠
Group Theory
Note that in terms of element multiplication
⎡1 0 0 ⎤ ⎡ − 1 0 0 ⎤ ⎡ − 1 0 0 ⎤
σ v C 2 = ⎢0 − 1 0⎥ ⎢ 0 − 1 0⎥ = ⎢ 0 1 0⎥ = σ'v
⎢ ⎥⎢ ⎥ ⎢ ⎥
⎢⎣0 0 1⎥⎦ ⎢⎣ 0 0 1⎥⎦ ⎢⎣ 0 0 1⎥⎦
So that the group multiplication table becomes
E C2 σv σ'v
E E C2 σv σ'v
C2 A E σ'v σv
σv σv σ'v E C2
σ'v σ'v σv C2 E
Group Theory
For water if we actually include the effects of the symmetry
operation on each atom, we will necessarily generate a 9 x 9
matrix, viz for C2
⎛ x1' ⎞ ⎡ 0 0 0 −1 0 0 0 0 0 ⎤ ⎛ x1 ⎞
⎜ '⎟ ⎢ ⎥ ⎜ ⎟
⎜ y1 ⎟ ⎢ 0 0 0 0 −1 0 0 0 0 ⎜ y1 ⎟

⎜ z' ⎟ ⎢ 0 0 0 0 0 1 0 0 0 ⎥⎜ z1 ⎟
⎜ 1' ⎟ ⎢ ⎥ ⎜ ⎟
⎜ x 2 ⎟ ⎢− 1 0 0 0 0 0 0 0 0 ⎜ x2 ⎟

⎜ y' ⎟ = ⎢ 0 −1 0 0 0 0 0 0 0 ⎥⎜ y 2 ⎟
⎜ 2⎟ ⎢ ⎥⎜ z ⎟
⎜ z '2 ⎟ ⎢ 0 0 1 0 0 0 0 0 0 ⎥⎜ 2 ⎟
⎜ '⎟ ⎢ 0 0 0 0 0 0 −1 0 0 ⎥⎜ x 3 ⎟
⎜ x3 ⎟ ⎢ ⎥⎜ ⎟
⎜ y3' ⎟ ⎢ 0 0 0 0 0 0 0 −1 0 ⎥⎜ y3 ⎟
⎜ ' ⎟ ⎢
⎝ z3 ⎠ ⎣ 0 0 0 0 0 0 0 0 1 ⎥⎦⎜⎝ z 3 ⎟⎠
Group Theory
The matrices within the matrix are called the irreducible
representations.

⎛ x1' ⎞ ⎡ 0 0 0 −1 0 0 0 0 0 ⎤ ⎛ x1 ⎞
⎜ '⎟ ⎢ ⎥ ⎜ ⎟
⎜ y1 ⎟ ⎢ 0 0 0 0 −1 0 0 0 0 ⎜ y1 ⎟

⎜ z' ⎟ ⎢ 0 0 0 0 0 1 0 0 0 ⎥⎜ z1 ⎟
⎜ 1' ⎟ ⎢ ⎥ ⎜ ⎟
⎜ x 2 ⎟ ⎢− 1 0 0 0 0 0 0 0 0 ⎜ x2 ⎟

⎜ y' ⎟ = ⎢ 0 −1 0 0 0 0 0 0 0 ⎥⎜ y 2 ⎟
⎜ 2⎟ ⎢ ⎥⎜ z ⎟
⎜ z '2 ⎟ ⎢ 0 0 1 0 0 0 0 0 0 ⎥⎜ 2 ⎟
⎜ '⎟ ⎢ 0 0 0 0 0 0 −1 0 0 ⎥⎜ x 3 ⎟
⎜ x3 ⎟ ⎢ ⎥⎜ ⎟
⎜ y3' ⎟ ⎢ 0 0 0 0 0 0 0 −1 0 ⎥⎜ y3 ⎟
⎜ ' ⎟ ⎢
⎝ z3 ⎠ ⎣ 0 0 0 0 0 0 0 0 1 ⎥⎦⎜⎝ z 3 ⎟⎠
Group Theory
Some rules regarding irreducible representations.

1. The sum of the squares of the dimensions of the


irreducible representations is equal to the order of the
group
∑ l i = l 1 + l 2 + l 3 + ... = h
2 2 2 2

2. The sum of the squares of the characters in any


irreducible representation equals h, that is
p2
∑ χ =hi
p
Group Theory
Some rules regarding irreducible representations.

3. The vectors whose components are the characters of two


different irreducible representations are orthogonal viz
∑ i χ j = 0 for i ≠ j
χ p p

p
4. In a given representation, the characters of all matrices
belonging to operations in the same class are identical.
5. The number of irreducible representations of a group is
equal to the number of classes in the group
∑ i χ j g p = hδij
χ p p

p
where gp gives the number of elements in the pth class.
Group Theory
How does this apply to the water molecule?

The group C2v consists of four elements. Each of these


elements represents a separate class. Based on rule #5,
there must be four irreducible representations for the
group.
From rule #1, we must also recognize that the sum of
squares of the dimension for these irreducible
representations is
∑ i
l 2
= l 2
1 + l 2
2 + l 2
3 + l 4 = 4
2

The only solution to this expression is


l1 = l 2 = l 3 = l 4 = 1
Group Theory
Thus the group C2v will have four one-dimensional
irreducible representations. This result implies that the
characters (i.e. the sum of the diagonal matrix elements)
for the four irreducible representations are in this case
the representations themselves (because the matrix
dimension is 1 x 1)! Based on this analysis, one
possible irreducible representation is

E C2 σv σ'v
Γ1 1 1 1 1

Note that this representation does satisfy rule #2 viz


p2
∑ χ =4
i
p
Group Theory
Since all other irreducible representations must also satisfy
this rule, each of the other representations will
necessarily need to have χiP ‘s with values of either +/-
1.
E C2 σ v σ'v
Γ1 1 1 1 1
Γ2 1 −1 −1 1
Γ3 1 −1 1 −1
Γ4 1 1 −1 −1
Group Theory
Note that all of the representations
are orthogonal to one another as E C2 σ v σ'v
required by rule #3. Γ1 1 1 1 1
Γ1 • Γ2 = 0, etc. Γ2 1 −1 −1 1
Γ3 1 −1 1 −1
Γ4 1 1 −1 −1

Fortunately for us, we will not have to generate a table for each
molecule we encounter like we did for water. Such tables,
known as character tables, are available from a variety of
sources including Appendix B in the text. What is important
from our perspective is that we know how to utilize the tables.
Group Theory
You will notice that the character table for C2v in the McQuarrie
text differs somewhat from the one we generated. For example,
there are no Γ symbols in textbook’s table. Instead, he uses the
letters A and B. This notation is actually known as the Mulliken
notation. A and B are used to designate one dimensional
representations. The letter E is used to designate two
dimensional representation and the letter T or F, a three
dimensional representation.
E C2 σ v σ'v
Γ1 1 1 1 1
Γ2 1 −1 −1 1
Γ3 1 −1 1 −1
Γ4 1 1 −1 −1
Group Theory
The only difference between A and B designations is that A
indicates the representation is symmetric WRT rotation about
the principal axis of rotation and B indicates the representation
is antisymmetric.

E C2 σ v σ '
v There is some additional
information in the tables that is
A1 1 1 1 1
not contained in ours.
A2 1 1 −1 −1 Specifically, there are some
B1 1 −1 1 −1 symbols, x,y,z, xx, xy, Rx, etc.
What in the world do these mean?
B2 1 −1 −1 1
Group Theory
E C2 σ v σ'v
A1 1 1 1 1 z x 2 ; y2 ; z2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y, R x yz
The x, y, and z are coordinate labels, the Ri indicate rotations and
the cross terms are related to polarizabilities. The question is,
why are these symbols assigned to specific irreducible
representations? The answer is based on the concept of a
mathematical transformation. We would say, e.g that the z-
coordinate transforms according to A1.
Group Theory
Back to our original motivation for exploring group theory. What
is the symmetry associated with the normal modes of water?
Again, we start by first considering what happens to the individual
coordinate vectors on each atom and determine the character for
each element.
Group Theory
For C2 ⎡ 0 0 0 −1 0 0 0 0 0⎤
⎢ 0 0 0 0 −1 0 0 0 0⎥
⎢ ⎥
⎢ 0 0 0 0 0 1 0 0 0⎥
⎢− 1 0 0 0 0 0 0 0 0 ⎥
⎢ ⎥
⎢ 0 −1 0 0 0 0 0 0 0⎥
⎢ ⎥
⎢ 0 0 1 0 0 0 0 0 0⎥
⎢ 0 0 0 0 0 0 −1 0 0⎥
⎢ ⎥
⎢ 0 0 0 0 0 0 0 −1 0⎥
⎢⎣ 0 0 0 0 0 0 0 0 1 ⎥⎦

χ C2
= −1
Group Theory
For σv
⎡ 0 0 0 −1 0 0 0 0 0⎤
⎢ 0 0 0 0 1 0 0 0 0⎥
⎢ ⎥
⎢ 0 0 0 0 0 1 0 0 0⎥
⎢− 1 0 0 0 0 0 0 0 0⎥
⎢ ⎥
⎢ 0 1 0 0 0 0 0 0 0⎥
⎢ ⎥
⎢ 0 0 1 0 0 0 0 0 0⎥
⎢ 0 0 0 0 0 0 −1 0 0⎥
⎢ ⎥
⎢ 0 0 0 0 0 0 0 1 0⎥
⎢⎣ 0 0 0 0 0 0 0 0 1 ⎥⎦
σ2
χ =1
Group Theory
For σv’
⎡− 1 0 0 0 0 0 0 0 0⎤
⎢ 0 1 0 0 0 0 0 0 0⎥
⎢ ⎥
⎢ 0 0 1 0 0 0 0 0 0⎥
⎢ 0 0 0 −1 0 0 0 0 0⎥
⎢ ⎥
⎢ 0 0 0 0 1 0 0 0 0⎥
⎢ ⎥
⎢ 0 0 0 0 0 1 0 0 0⎥
⎢ 0 0 0 0 0 0 −1 0 0⎥
⎢ ⎥
⎢ 0 0 0 0 0 0 0 1 0⎥
⎢⎣ 0 0 0 0 0 0 0 0 1 ⎥⎦
σ'v
χ =3
Group Theory
For E
⎡1 0 0 0 0 0 0 0 0⎤
⎢0 1 0 0 0 0 0 0 0⎥
⎢ ⎥
⎢0 0 1 0 0 0 0 0 0⎥
⎢0 0 0 1 0 0 0 0 0 ⎥
⎢ ⎥
⎢0 0 0 0 1 0 0 0 0⎥
⎢ ⎥
⎢0 0 0 0 0 1 0 0 0⎥
⎢0 0 0 0 0 0 1 0 0⎥
⎢ ⎥
⎢0 0 0 0 0 0 0 1 0⎥
⎢⎣0 0 0 0 0 0 0 0 1 ⎥⎦
χE = 9
Group Theory
In terms of the cartesian coordinates, we now have the reducible
representation

E C2 σv σ'v
A1 1 1 1 1 z x 2 ; y2 ; z2
A2 1 1 −1 −1 Rz xy
B1 1 −1 1 −1 x, R y xz
B2 1 −1 −1 1 y, R x yz
Γcart 9 −1 1 3
We are interested in a quantity called the direct sum which will
tell us how Γcart is related to the irreducible representations. To
determine this quantity, we will need to “reduce” Γcart.
Group Theory
The standard formula for reduction is

1 N C Cn
mα = ∑ χ g n χα Cn

h n =1
N c is number of classes in the group
gn is number of elements in the nth class
χ Cn is character of the nth reducible representation
χ Cα n is character of the nth irreducible representation
Group Theory
Thus we have
1
m A1 = [9 ⋅1 ⋅1 + (−1) ⋅1 ⋅1 + 1 ⋅1 ⋅1 + 3 ⋅1 ⋅1] = 3
4
1
m A 2 = [9 ⋅1 ⋅1 + (−1) ⋅1 ⋅1 + 1 ⋅1 ⋅ (−1) + 3 ⋅1 ⋅ (−1)] = 1
4
1
m B1 = [9 ⋅1 ⋅1 + (−1) ⋅1 ⋅ (−1) + 1 ⋅1 ⋅1 + 3 ⋅1 ⋅ (−1)] = 2
4
1
m B2 = [9 ⋅1 ⋅1 + (−1) ⋅1 ⋅ (−1) + 1 ⋅1 ⋅ (−1) + 3 ⋅1 ⋅1] = 3
4

⇒ Γcart = 3A1 + A 2 + 2B1 + 3B2


Group Theory
From the character table we know that
Γrot ,trans = A1 + A 2 + 2B1 + 2B2
Which suggests that the direct sum for the vibrational degrees of
freedom is

Γvib = Γcart − Γrot ,trans = 2A1 + B2

We can take this analysis a step further and ask, “how are these
vibrational symmetries related to the displacement of the
individual atoms?” First however, we need to define some
internal coordinates for the molecule.
Group Theory
We will define the internal coordinates as follows
C2

r1 r2
α
σv’
σv

Using this labeling scheme, we note that the character


representation is
Group Theory
E C2 v σv σ'v
Γr 2 0 0 2
Γα 1 1 1 1
⎡ r1' ⎤ ⎡1 0 0⎤ ⎡ r1 ⎤ ⎡ r1' ⎤ ⎡0 1 0⎤ ⎡ r1 ⎤
E ⎢ '⎥ σv ⎢ ' ⎥
Γ : ⎢r2 ⎥ = ⎢0 1 0⎥ ⎢r2 ⎥ Γ : ⎢r2 ⎥ = ⎢1 0 0⎥ ⎢r2 ⎥
⎢ ⎥⎢ ⎥ ⎢ ⎥⎢ ⎥
⎢⎣α ⎥⎦ ⎢⎣0 0 1⎥⎦ ⎢⎣α ⎥⎦ ⎢⎣α ⎥⎦ ⎢⎣0 0 1⎥⎦ ⎢⎣α ⎥⎦

⎡ r1' ⎤ ⎡0 1 0⎤ ⎡ r1 ⎤ ⎡ r1' ⎤ ⎡1 0 0⎤ ⎡ r1 ⎤
C2 ⎢ ' ⎥ σ 'v ⎢ ' ⎥
Γ : ⎢r2 ⎥ = ⎢1 0 0⎥ ⎢r2 ⎥ Γ : ⎢r2 ⎥ = ⎢0 1 0⎥ ⎢r2 ⎥
⎢ ⎥⎢ ⎥ ⎢ ⎥⎢ ⎥
⎢⎣α ⎥⎦ ⎢⎣0 0 1⎥⎦ ⎢⎣α ⎥⎦ ⎢⎣α ⎥⎦ ⎢⎣0 0 1⎥⎦ ⎢⎣α ⎥⎦
Group Theory
E C2 v σv σ'v
Γr 2 0 0 2
Γα 1 1 1 1
Using a standard reduction formula, we get for the Γr

1
m A1 = [2 ⋅1 ⋅1 + 0 ⋅1 ⋅1 + 0 ⋅1 ⋅1 + 2 ⋅1 ⋅1] = 1
4
1
m A 2 = [2 ⋅1 ⋅1 + 0 ⋅1 ⋅1 + 0 ⋅1 ⋅ (−1) + 2 ⋅1 ⋅ (−1)] = 0
4
1
m B1 = [2 ⋅1 ⋅1 + 0 ⋅1 ⋅ (−1) + 0 ⋅1 ⋅1 + 2 ⋅1 ⋅ (−1)] = 0
4
1
m B2 = [2 ⋅1 ⋅1 + 0 ⋅1 ⋅ (−1) + 0 ⋅1 ⋅ (−1) + 2 ⋅1 ⋅1] = 1
4
Group Theory
E C2 v σv σ'v
Γr 2 0 0 2
Γα 1 1 1 1
Using this same reduction procedure for both internal
coordinates yields

Γr = A1 + B2 Γα = A1

Thus, the three normal modes of water consist of one mode of


B2 symmetry, which is a pure OH stretching mode and two
modes of A1 symmetry, which contain a combination of OH
stretch and H-O-H bond deformation in both modes.
Group Theory

Molecular Spectra and Molecular Structure II. Infrared and


Raman Spectra of Polyatomic Molecules, G. Herzberg, FRSC,
Van Nostrand Company, Inc, Princeton, NJ (1945).
Group Theory
Procedure for determining how many genuine normal modes of
vibration for a molecule.

1. Generate the reducible representations by applying the


operations of the group to the Cartesian displacement vectors.
2. From the list generated symmetry types (which contain both
genuine and non-genuine modes), remove the translational and
rotational components using information in the character tables.
3. This final list of irreducible representations represents a sum of
the number of genuine normal modes for the molecule.
4. The sum of the dimensions of the irreducible representations on
this list equals the number of normal modes of vibration for the
molecule and there will be a normal mode having symmetry
corresponding to each of the irreducible representations on the
list.