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 m k k

x1

x2

x3

Molecular Vibrations
From a classical physics standpoint, M 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 for each mass in terms of Newtons Second Law, viz m k M

x2

x3

M&&3 = − k ( x 3 − x 2 ) x

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

Molecular Vibrations
From a classical physics standpoint, 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 for each mass in terms of Newton’s Second Law, viz M k m k M

x1

x2

x3

M&&3 = − k ( x 3 − x 2 ) x

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

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. 0eiωt . . ω. will be of the form this function into our earlier expression leads to k ω x1 = ( x1 − x 2 ) M k k 2 ω x 2 = ( x 2 − x1 ) + ( x 2 − x 3 ) m m k 2 ω x3 = (x 3 − x 2 ) M 2 where the common factor eiωt has been divided out. Inserting the normal modes. in terms of x i = x i .

Molecular Vibrations These three expressions represent a system of equations that can be cast in matrix form k ⎛ k − ⎜ M ⎜ M ⎜ − k 2k ⎜ m m k ⎜ ⎜ 0 − M ⎝ ⎞ 0 ⎟ ⎛ x1 ⎞ ⎟⎛ x1 ⎞ ⎜ ⎟ k ⎟⎜ ⎟ 2 − ⎜ x2 ⎟ = ω ⎜ x2 ⎟ m ⎟⎜ ⎟ ⎜x ⎟ x3 ⎠ k ⎟⎝ ⎝ 3⎠ ⎟ M ⎠ .

viz k 2 −ω M k − m 0 k − M 2k − ω2 m k − M 0 k − =0 m k − ω2 M .Molecular Vibrations We can cast this expression in the form of a secular determinant.

x2 and x3 we simply need to insert these eigenvalues back into the system of equations. ω = + M m M 2 2 To solve for x1. ω = .Molecular Vibrations Which can be factored to give ⎛ k − ω2 ⎞⎛ ω2 − 2k − k ⎞ = 0 ω⎜ ⎟⎜ ⎟ m M⎠ ⎝M ⎠⎝ 2 giving rise to the eigenvalues k 2k k 2 ω = 0. .

Thus ω2 = 0 describes pure translation of the molecule.Molecular Vibrations For example. we find that x1 = x3 and x2 = -2Mx1/m. ω2 = 0 leads to x1 − x2 − x3 + x3 =0 =0 =0 − x1 + 2 x 2 − x2 Which in turn yields. Those of you that have been through the undergrad Pchem course here recognize that CO2 also possesses two degenerate bending modes. However. This last eigenvalue thus corresponds to the asymmetric stretch of CO2. we restricted ourselves here to just the x-axis. Finally. You should convince yourself that ω2= k/M leads to x1= -x3 and x2 = 0 or the symmetric stretch of CO2. x1 = x2 = x3. . for ω2= k/M + 2k/m.

Molecular Vibrations Graphically. we would say that the normal modes for carbon dioxide are .

The use of symmetry involves a branch of mathematics known as group theory. could get quite involved. .Molecular Vibrations You can imagine that for more complicated (larger) molecules. In many cases. performing an analysis. we can take advantage of symmetry in the molecule to simply this analysis. such as we just did.

2. by convention. is given the label E. the elements may not commute. a group is nothing more than a collection of elements that are interrelated by a certain set of rules. BA will not necessarily be C. What are these rules? 1. what is a group? Mathematically. This element is generally known as the identity element and. AE = EA = A. At least one element in the group must commute with all other elements.Group Theory First of all. The product of any two elements and the square of any element must also be members of the group. Symbolically. . Note however that will AB = C. In other words.

the order is represented by the symbol h. Often.Group Theory 3. 4. Groups may be either finite or infinite. A(BC)=(AB)C. the number of elements is referred to as the order of the group. Now. The associative law of multiplication must hold. and we know what all of the products are. By definition.. . For finite groups. then the group is said to be completely and uniquely defined. i.e. if we have a complete and non-redundant list of elements for a finite group. A is the reciprocal of B if AB = E. Every element must have a reciprocal. which is also a member of the group.

For example. B and E.Group Theory A convenient way to present all of the information about the group is through the use of a group multiplication table. lets say that we have a group with the elements A. We can construct a multiplication table as shown below E E A B E A B A A B B .

to complete the table. Assuming the former. either AA=B or AA=E. having two identical rows or two identical columns is not allowed. E E A B E A B A A B E B B E B Thus. In other words. 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.Group Theory To complete the table. we would write .

Group Theory In any group. . it is of course possible to identify subgroups. the identity element is a group of order 1. we say that a complete set of elements which are conjugate to one another represents a class of the group. these sets are called classes. In group theory. 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. For example. If the group can be divided into smaller sets.

from our perspective. One could argue that group theory. but we can identify symmetry operations for any molecule. is nothing more than a means to apply some formal mathematical criteria to the concept of molecular symmetry. We will see that such an identification leads to a powerful analysis capability. . In other words.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. we are interested in identifying the set of symmetry operations for a particular molecule as a mathematical group.

σv’. σv. lets work out the group theory representation for water. . C2v.Group Theory To begin with. 3 1 2 What are the symmetry operations for this molecule? E.

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

Group Theory ⎛ x'⎞ ⎛ x ⎞ ⎡1 0 0 ⎤ ⎛ x ⎞ ⎜ ⎟ ⎜ ⎟ ⎢ ⎥⎜ y ⎟ ⎜ y ' ⎟ = σ v ⎜ y ⎟ = ⎢0 − 1 0 ⎥ ⎜ ⎟ ⎜ z' ⎟ ⎜ z ⎟ ⎢0 0 1 ⎥ ⎜ z ⎟ ⎝ ⎠ ⎝ ⎠ ⎣ ⎦⎝ ⎠ 2 3 1 ⎛ x'⎞ ⎛ x ⎞ ⎡ − 1 0 0⎤ ⎛ x ⎞ ⎜ ⎟ ⎜ ⎟ ⎢ ' ⎥⎜ y ⎟ ⎜ y' ⎟ = σ v ⎜ y ⎟ = ⎢ 0 1 0⎥ ⎜ ⎟ ⎜ 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 E C2 σv E A σv C2 C2 E σv σv E C2 σ'v σ'v σ'v σv C2 E σ'v σ'v σ σv ' v .

' ⎛ x1 ⎞ ⎡ 0 ⎜ '⎟ ⎢ ⎜ y1 ⎟ ⎢ 0 ⎜ z' ⎟ ⎢ 0 ⎜ 1⎟ ⎢ ' ⎜ x 2 ⎟ ⎢− 1 ⎜ y' ⎟ = ⎢ 0 ⎜ 2⎟ ⎢ ⎜ z '2 ⎟ ⎢ 0 ⎜ '⎟ ⎢ 0 x3 ⎟ ⎜ ⎢ ' ⎜ y3 ⎟ ⎢ 0 ⎜ ' ⎟ ⎢ ⎝ z3 ⎠ ⎣ 0 For water if we actually include the effects of the symmetry operation on each atom. viz for C2 Group Theory 0 0 0 0 0 −1 0 −1 0 0 0 0 0 1 0 0 0 0 0 0 −1 0 0 0 0 0 0 0 0 0 0 0 0 0 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 −1 0 0 ⎤ ⎛ x1 ⎞ ⎥⎜ y ⎟ 0 ⎜ 1⎟ ⎥ 0 ⎥⎜ z1 ⎟ ⎥⎜ x ⎟ 0 ⎜ 2⎟ ⎥ 0 ⎥⎜ y 2 ⎟ ⎥⎜ z ⎟ 0 ⎥⎜ 2 ⎟ 0 ⎥⎜ x 3 ⎟ ⎥⎜ ⎟ 0 ⎥⎜ y3 ⎟ 1 ⎥⎜ z 3 ⎟ ⎦⎝ ⎠ . we will necessarily generate a 9 x 9 matrix.

The matrices within the matrix are called the irreducible representations. ' ⎛ x1 ⎞ ⎡ 0 ⎜ '⎟ ⎢ ⎜ y1 ⎟ ⎢ 0 ⎜ z' ⎟ ⎢ 0 ⎜ 1⎟ ⎢ ' ⎜ x 2 ⎟ ⎢− 1 ⎜ y' ⎟ = ⎢ 0 ⎜ 2⎟ ⎢ ⎜ z '2 ⎟ ⎢ 0 ⎜ '⎟ ⎢ 0 x3 ⎟ ⎜ ⎢ ' ⎜ y3 ⎟ ⎢ 0 ⎜ ' ⎟ ⎢ ⎝ z3 ⎠ ⎣ 0 Group Theory 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 −1 0 0 0 0 0 0 0 0 0 0 −1 0 0 0 0 0 0 0 0 0 −1 0 0 ⎤ ⎛ x1 ⎞ ⎥⎜ y ⎟ 0 ⎜ 1⎟ ⎥ 0 ⎥⎜ z1 ⎟ ⎥⎜ x ⎟ 0 ⎜ 2⎟ ⎥ 0 ⎥⎜ y 2 ⎟ ⎥⎜ z ⎟ 0 ⎥⎜ 2 ⎟ 0 ⎥⎜ x 3 ⎟ ⎥⎜ ⎟ 0 ⎥⎜ y3 ⎟ 1 ⎥⎜ z 3 ⎟ ⎦⎝ ⎠ .

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 2 2 2 2 Group Theory ∑ l i = l 1 + l 2 + l 3 + . that is ∑ χ =h p p2 i .. The sum of the squares of the characters in any irreducible representation equals h.. = h 2.

Some rules regarding irreducible representations. . In a given representation. The vectors whose components are the characters of two different irreducible representations are orthogonal viz p p ∑ χi χ j = 0 for i ≠ j p Group Theory 4. the characters of all matrices belonging to operations in the same class are identical. 5. 3. The number of irreducible representations of a group is equal to the number of classes in the group p p ∑ χi χ j g p = hδij p where gp gives the number of elements in the pth class.

Each of these elements represents a separate class. there must be four irreducible representations for the group. we must also recognize that the sum of squares of the dimension for these irreducible representations is 2 2 2 2 2 ∑ l i = l1 + l 2 + l 3 + l 4 = 4 The only solution to this expression is l1 = l 2 = l 3 = l 4 = 1 . From rule #1. Based on rule #5.Group Theory How does this apply to the water molecule? The group C2v consists of four elements.

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. This result implies that the characters (i.Group Theory Thus the group C2v will have four one-dimensional irreducible representations. one possible irreducible representation is Γ1 E C2 1 1 p2 i σv 1 σ'v 1 Note that this representation does satisfy rule #2 viz ∑ χ =4 p .e.

Γ1 Γ2 Γ3 Γ4 E C2 σ v σ'v 1 1 1 1 1 −1 −1 1 1 −1 1 −1 1 1 −1 −1 .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.

are available from a variety of sources including Appendix B in the text.Group Theory Note that all of the representations are orthogonal to one another as required by rule #3. etc. . Such tables. Γ1 Γ2 Γ3 Γ4 E C2 σ v σ'v 1 1 1 1 1 −1 −1 1 1 −1 1 −1 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. known as character tables. What is important from our perspective is that we know how to utilize the tables. Γ1 • Γ2 = 0.

For example.Group Theory You will notice that the character table for C2v in the McQuarrie text differs somewhat from the one we generated. This notation is actually known as the Mulliken notation. Instead. a three dimensional representation. Γ1 Γ2 Γ3 Γ4 E C2 σ v σ'v 1 1 1 1 1 −1 −1 1 1 −1 1 −1 1 1 −1 −1 . 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. there are no Γ symbols in textbook’s table. he uses the letters A and B.

y. Specifically. Rx. xx. etc. What in the world do these mean? . A1 A2 B1 B2 E C2 σ v σ'v 1 1 1 1 1 1 −1 −1 1 −1 1 −1 1 −1 −1 1 There is some additional information in the tables that is not contained in ours.z. xy.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. there are some symbols. x.

and z are coordinate labels. R y y. y. z2 xy xz yz The x. why are these symbols assigned to specific irreducible representations? The answer is based on the concept of a mathematical transformation. the Ri indicate rotations and the cross terms are related to polarizabilities. .g that the zcoordinate transforms according to A1. We would say. The question is.Group Theory A1 A2 B1 B2 E C2 σ v σ'v 1 1 1 1 1 1 −1 −1 1 −1 1 −1 1 −1 −1 1 z Rz x. R x x 2 . e. y2 .

. 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 Back to our original motivation for exploring group theory.

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 −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⎥ ⎥ 0⎥ ⎥ 0⎥ 0⎥ ⎥ 0⎥ 1⎥ ⎦ χ C2 = −1 .

For σv Group Theory ⎡ 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 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⎥ ⎥ 0⎥ ⎥ 0⎥ 0⎥ ⎥ 0⎥ 1⎥ ⎦ χσ2 = 1 .

For σv’ Group Theory ⎡− 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⎥ ⎦ χ σ'v =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 .

R y y. R x x 2 . . y2 .In terms of the cartesian coordinates. we now have the reducible representation Group Theory σv 1 1 1 σ ' v E C2 A1 A2 B1 B2 Γcart 1 1 1 1 1 1 −1 1 −1 1 3 z Rz x. z2 xy xz yz −1 −1 −1 −1 9 −1 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.

The standard formula for reduction is Group Theory 1 N C Cn m α = ∑ χ g n χ Cn α 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 Cn is character of the nth irreducible representation α .

Thus we have Group Theory 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 .

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.From the character table we know that Group Theory Γrot . . “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.

We will define the internal coordinates as follows C2 Group Theory r1 α σv’ σv r2 Using this labeling scheme. we note that the character representation is .

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

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 Γr Γα E C2 v 2 0 1 1 σv 0 1 σ'v 2 1 Using a standard reduction formula.

.Group Theory Γr Γα E C2 v 2 0 1 1 σv 0 1 σ'v 2 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 contain a combination of OH stretch and H-O-H bond deformation in both modes. which is a pure OH stretching mode and two modes of A1 symmetry.

G.Group Theory Molecular Spectra and Molecular Structure II. NJ (1945). FRSC. Van Nostrand Company. Infrared and Raman Spectra of Polyatomic Molecules. Princeton. Inc. . Herzberg.

Group Theory Procedure for determining how many genuine normal modes of vibration for a molecule. 2. 1. 3. 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. remove the translational and rotational components using information in the character tables. This final list of irreducible representations represents a sum of the number of genuine normal modes for the molecule. . From the list generated symmetry types (which contain both genuine and non-genuine modes). Generate the reducible representations by applying the operations of the group to the Cartesian displacement vectors. 4.

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