Chemistry 431

Lecture 13 Group Theory Symmetry Operations Properties of a Group Point Groups Reducible Representations NC State University

Definition of a Symmetry Operation

Symmetry operation: an operation that moves a molecule into a new orientation that appears equivalent to the original one. Example: rotation by 2/3 A C3 C

(In general, Cn is a rotation by 2/n)

Definition of a Symmetry Element

Symmetry element: a point line or plane with respect to which the symmetry operation is performed. Example: the B-F1 bond can be defined as an element.
F1
F3

C3

F3

F2

F2

F1

Note that the rotated molecule is indistinguishable.

Operations: The Identity Operation

The identity operation is given the symbol E. It simply means that there is no change in the position of the molecule or object.

F1

F1

F3

F2

F3

F2

Reflection through a Plane

The reflection operation is given the symbol . Note that for the example of BF3 given below the effect of vertical mirror plane about the symmetry element B-F1 is to reverse the position of atoms F2 and F3.
F1

F1

F3

F2

F2

F3

Two Types of Reflection Plane

In this case the reflection is perpendicular to another possible reflection plane shown in this diagram. We can define two symmetry planes shown as: 1. The horizontal reflection plane, which has symbol h. 2. The vertical reflection plane, which has symbol v.
F1

F3

F2

The horizontal reflection plane

The horizontal reflection plane does not change the position of any of the atoms in BF3 since all of the atoms are in the mirror plane.

F1

F1

F3

F2

F3

F2

The horizontal reflection plane

We can see a case where the horizontal plane of reflection results in a change in the two axial carbonyls, but not the equatorial carbonyls. axial
CO1 CO2 O 4C Fe CO3 CO5

CO5

h
CO2 O4C Fe CO3 CO1

equatorial

The vertical reflection plane

To complete this introduction to reflection planes we can consider the effect of a vertical reflection on Fe(CO)5. In This case we have defined the symmetry element as the Plane containing CO1, CO3 and CO5. axial
CO1
CO1

v
CO2 O4 C Fe CO3 equatorial CO5
CO5 CO4 O2C Fe CO3

Note that CO2 and CO4 switch positions as a result.

Rotations in Fe(CO)5
Just as there are two types of reflection plane in Fe(CO)5 We can also define two types of rotation shown below. C3 axial C2

CO1 CO2 O4 C Fe CO3 CO5

equatorial

Definition of Inversion
Inversion, i involves passing each atom through the center of the molecule. If an atom has coordinate (x,y,x) then it has coordinates (-x,-y,-z) after inversion. This only works if the molecule has a center of symmetry. Fe(CO)5 does not have a center of symmetry.

CO1 CO2 O4 C Fe CO3

No inversion possible!

CO5

Example of Inversion
A molecule such as Mo(CO)6 does have a center of symmetry and can be inverted as shown below.
CO1 O5C Mo O4C CO6 CO3
O2C CO1

CO2

CO6 O3C Mo CO5 CO4

Improper rotation
An improper rotation is a combined rotation followed by A reflection about a plane perpendicular to the axis of rotation. It is given the symbol Sn, where n is order of the rotation.

S4

H1 C H2 C C

H3 H4

H4 C H3 C C

H1 H2

Multiple applications of symmetry operations

A symmetry operation can be applied multiple times. For example a C3 rotation may be applied twice. Returning to BF3 we can consider C32 rotation, which consists of two Applications of the C3 rotation. First application from before.
F1

C3

F3

F3

F2

F2

F1

Multiple applications of symmetry operations

A symmetry operation can be applied multiple times. For example a C3 rotation may be applied twice. Returning to BF3 we can consider C32 rotation, which consists of two Applications of the C3 rotation. C32 = C3C3
F1

C32

F2

F3

F2

F1

F3

The product of multiple symmetry operations can give the identity

If we apply the C3 rotation one more time (for a total of three applications) the geometry returns to the starting structure. In other words we can write: C33 = C3C3C3 = E
F1 F1

C33 = E

F3

F2

F3

F2

The order of operation matters

In general the order of operation will affect the final result. In this case the operators do not commute.
CO1 CO2 O 4C Fe CO3 CO5 CO1 CO2 O 4C Fe CO3 CO5

CO1

vC3
CO2 O 3C Fe CO4 CO5 CO1

C3v
O3C Fe

CO4 CO2 CO5

Groups

Properties of a group
1. There must exist an identity operator which commutes with all other operators. 2. The product of any two operators must also be a member of the group. 3. Multiplication is associative, but not necessarily commutative. 4. There must exist an inverse (or reciprocal) for each element in the group. Corollaries: 1. The identity operator is its own inverse. 2. A similarity transform is an operation: Z-1XZ = Y

Point groups
We can assemble the operations of the group into a multiplication table. This group of operations satisifes all of the requirements of a mathematical group and is called a point group. Point groups get their name from the fact that at least one point in space remains unchanged for all operations in the group. C1 is a point group whose only symmetry operation is E, the identity. In other words there is no symmetry. Cs is a point group whose symmetry operations are E and . The symmetry is restricted to a mirror plane.

Point group examples C1 and Cs

We can assemble the operations of the group into a multiplication table. This group of operations satisifes all of the requirements of a mathematical group and is called a point group. Point groups get their name from the fact that at least one point in space remains unchanged for all operations in the group. C1 is a point group whose only symmetry operation is E, the identity. In other words there is no symmetry. Cs is a point group whose symmetry operations are E and . The symmetry is restricted to a mirror plane.

Point group examples C1 and Cs

C1 Cs

N Cl
E only

H F

N H
E and

H F

Point group examples C1 and Cs

C1 Cs

N Cl
E only

H F

N H
E and

H F

Point group example: Ammonia C3v

N H H H
The symmetry operation E exists for all groups.

Point group example: Ammonia C3v

N H
A vertical reflection plane v is shown. There are three such planes in molecules in the C3v point group.

H H

Point group example: Ammonia C3v

N H H H
There are two possible Rotations about a 3-fold axis. The first is a 120o rotation and the second is a 240o rotation.

Point group example: Ammonia C3v

N H H H
The group consists of these three symmetry operations. The order of the group is h=6. There are three irreducible representations in the point group C3v, which are given in the character table below.

Similarity Transform
The operations X and Y are said to be conjugate if they are related by a similarity transform Z-1XZ = Y where Z is at least one member of the group. A class is a complete set of operations that are conjugate to each other. For example, in the point group C3v one can show that The operations C3 and C32 are in the same class. We note that (v)-1 = v

(v)-1 C3 v = v C3 v = v v= C32

v
2
2

C3 v

Point Groups
C1 : no symmetry Cs : only a plane of symmetry Ck : only a k rotational axis Ci : only an inversion center Ckh : a k rotational axis and h Ckv : a k rotational axis and k v Dk : only Ck and k C2 rotational axes Dkh : operations of Dk and h which implies k v Dkd : operations of Dk and k d which bisect the angles of C2 Sk : only the improper rotation Sk Td : tetrahedral Oh : octahedral

Systematic assignment of a molecule to a point group

Symmetry properties are used to determine the molecular orbitals and spectral features of a molecule. It is important to have a systematic approach to assignment of the point group. The scheme gives a systematic series of questions that lead to the point group assignment.

Examples of point group assignment

Determining the point group to which a molecule belongs will be the first step in a treatment of the molecular orbitals or spectra of a compound. It is important that this be done somewhat systematically. The flow chart in the figure is offered as an aid, and a few examples should clarify the process.

What are the point groups for the following Pt(II) ions?
Cl Pt Cl Cl Cl Pt Cl Br Cl 2Cl Pt Cl Cl Pt Br Br Cl 2Cl Pt Cl Cl Pt Cl Br 2-

What are the point groups for the following Pt(II) ions? Cl Cl Cl 2Cl Cl Cl 2Cl Cl Br 2Pt Cl Cl Pt Cl Br Pt Cl Pt Br Br Pt Cl Pt Cl

C B A A contains three C2 axes, i.e., [Ck?] is yes with k=2. It contains a plane of symmetry so [?] is yes. The three C2 axes are perpendicular, i.e, there is a C2 axis and two perpendicular C2's which means that [C2?] is yes. There is a plane of symmetry perpendicular to the C2 so [h?] is yes and we arrive at the D2h point group.

What are the point groups for the following Pt(II) ions? Cl Cl Cl 2Cl Cl Cl 2Cl Cl Br 2Pt Cl Cl Pt Cl Br Pt Cl Pt Br Br Pt Cl Pt Cl

C B A B contains only one C2 axis, no C2's, no h, but it does have two v's and is therefore a C2v ion.

What are the point groups for the following Pt(II) ions? Cl Cl Cl 2Cl Cl Cl 2Cl Cl Br 2Pt Cl Cl Pt Cl Br Pt Cl Pt Br Br Pt Cl Pt Cl

C B A C contains a single C2 axis and a horizontal plane (the plane of the ion) and therefore has C2h symmetry.

Matrix representation of groups

The basis is comprised by the labels attached to objects. For molecules the objects can be: 1. Atoms 2. Coordinates 3. Orbitals 4. Bonds 5. Angles The number of basis functions or labels is called the dimension. For example, when considering molecular motions we Can assign coordinates x, y and z to each atom. There are three coordinates for N atoms to give a total dimension of 3N.

z1 O z2 H y2 x2 y1 x1 z3 H y3 x3

C2(z)

z1 x1 y1 O x3 z3 y3 H z2 x2 y2 H

C2(z) gives (xi -xj), (yi -yj), and (zi +zj) where i = j for O coordinates since the O lies along C2 but i j for the H since they do not lie along C2 and are therefore rotated into one another, e.g., x2 -x3. We can represent this transformation in matrix notation where each atom will have a 3x3 matrix,
xi 1 0 0 x j x j yi = 0 1 0 y j = y j zi 0 0 +1 zj + zj

(3r x 3c)(3r x 1c) gives a (3r x 1c)

The trace of the matrix is the sum of the diagonal elements. In this case it is -1.

Motions of H2O
Since there are atoms the full matrix for H2O is a 9x9:

The hydrogen atoms are not on the diagonal since the atoms themselves are moved as a result of the C2 rotation. The trace of this matrix is 1. This is also called the character.

Motions of H2O
We can consider also the result of the v mirror plane, which is also a 9x9:

None of the atoms are moved by the symmetry operation so all of the submatrices representing the vectors lie along the diagonal. For this operation the trace (also known as the character) is +3.

Conclusions for symmetry operations

We can conclude with 2 general rules: 1. Only those atoms, which remain in the place following an operation can contribute to the trace. 2. Each atom contributes the same amount to the trace since all of the atoms have the same 3x3 matrix. Using these principles we can see that v has a character of +1. The identity always has a character equal to the number of basis functions. Here E = 9. Using the character of the 4 symmetry operations of the C2v point group we can construct a representation .

z1 O z2 H y2 x2 y1 x1 z3 H y3 x3

9x9 matrix for C2 rotation in H2O

x1 1 0 0 0 0 0 0 0 0 x1 y1 0 1 0 0 0 0 0 0 0 y1 z1 0 0 +1 0 0 0 0 0 0 z1 x 0 0 0 0 0 0 1 0 0 x 2 2 C2 y2 = 0 0 0 0 0 0 0 1 0 y2 z2 0 0 0 0 0 0 0 0 +1 z2 x 3 0 0 0 1 0 0 0 0 0 x3 y3 0 0 0 0 1 0 0 0 0 y3 z3 0 0 0 0 0 +1 0 0 0 z3

z1 O z2 H y2 x2 y1 x1 z3 H y3 x3

For v(yz), no atoms are moved so the matrix representation is

x1 1 0 0 0 0 0 0 0 0 x1 y1 0 + 1 0 0 0 0 0 0 0 y1 z1 0 0 + 1 0 0 0 0 0 0 z1 x 0 0 0 1 0 0 0 0 0 x 2 2 y2 = 0 0 0 0 + 1 0 0 0 0 y2 v z2 0 0 0 0 0 +1 0 0 0 z2 x3 0 0 0 0 0 0 1 0 0 x 3 y3 0 0 0 0 0 0 0 + 1 0 y 3 z 0 0 0 0 0 0 0 0 + 1 z 3 3

9x9 matrices (!) like those above could serve as the representations of the operations for the water molecule in this basis!

Fortunately, only the trace of this matrix is required. This sum is called the character, (R). Here, (v) = 3

x1 1 0 0 0 0 0 0 0 0 x1 y1 0 + 1 0 0 0 0 0 0 0 y1 z1 0 0 + 1 0 0 0 0 0 0 z1 x 0 0 0 1 0 0 0 0 0 x 2 2 y2 = 0 0 0 0 + 1 0 0 0 0 y2 v z2 0 0 0 0 0 +1 0 0 0 z2 x3 0 0 0 0 0 0 1 0 0 x 3 y3 0 0 0 0 0 0 0 + 1 0 y 3 z 0 0 0 0 0 0 0 0 + 1 z 3 3

For (C2) = -1

x1 1 0 0 0 0 0 0 0 0 x1 y1 0 1 0 0 0 0 0 0 0 y1 z1 0 0 +1 0 0 0 0 0 0 z1 x 0 0 0 0 0 0 1 0 0 x 2 2 C2 y2 = 0 0 0 0 0 0 0 1 0 y2 z2 0 0 0 0 0 0 0 0 +1 z2 x 3 0 0 0 1 0 0 0 0 0 x3 y3 0 0 0 0 1 0 0 0 0 y3 z3 0 0 0 0 0 +1 0 0 0 z3

-1

For a reflection through the plane bisecting the H-O-H bond angle, (v') = +1 since only the O is unshifted and a plane contributes +1 for each unshifted atom. The character for the identity element will always be the dimension of the basis since all labels are unchanged. For water then, (E) = 9.

The representation () for water in this Cartesian basis is:

E C2 v(yz) 9 -1 3

v'(xz) 1

Reducible and irreducible representations

We call the representation a reducible representation. Here we write the reducible representation as:

E C2 v(yz) 9 -1 3

v'(xz) 1

The irreducible representations form the basis of the point group in the same way that the vectors along x, y and z form the basis for three dimensional space. H2O belongs the point group C2v. In this point group There are 4 irreducible representations, A1, B1, A2, B2. The decomposition of the reducible representation is a Unique determination of the irreducible reps (or irreps)z spanned by .

s-Orbitals as a basis
I
II III

E each atom has 1 and not 3 labels so each operation is a 3x3 matrix as opposed to the 9x9 matrices of the previous basis. In addition, there can be no sign change for an sorbital. The resulting representation is,
1 0 E = 0 1 0 0 0 0 ; 1 1 0 C2 = 0 0 0 1 0 1 ; 0 1 0 v = 0 1 0 0 0 0 ; 1 1 0 ' v = 0 0 0 1 0 1 0

s-Orbitals as a basis
I
II III

E each atom has 1 and not 3 labels so each operation is a 3x3 matrix as opposed to the 9x9 matrices of the previous basis. In addition, there can be no sign change for an sorbital. The resulting representation is,
1 0 E = 0 1 0 0 0 0 ; 1 1 0 C2 = 0 0 0 1 0 1 ; 0 1 0 v = 0 1 0 0 0 0 ; 1 1 0 ' v = 0 0 0 1 0 1 0

Transformation of a basis
If one basis (f ') is a linear combination of another basis (f) or f ' = Cf, then the representation in one basis should be similar to that in the other. It can be shown that the matrix representations of operator R in these two basis sets (D(R) and D'(R)) are related by a similarity transformations: D'(R) = C-1D(R)C and D(R) = CD'(R)C-1 i.e., the matrices D(R) and D'(R) are conjugate.

I
II III

For example, the linear combination of s-orbitals: X = I + II Y = I + III Z = II + III which can be expressed in matrix form as:
X 1 1 0 I + 0.5 +0.5 0.5 1 Y = 1 0 1 II and inverse of C is C = + 0.5 0.5 + 0.5 Z 0 1 1 III 0.5 +0.5 + 0.5

f' =

The matrix representation of C2 (D'(C2)) in the new basis then is given by D'(C2) = C-1D(C2)C

C-1
+ 0.5 +0.5 or D'(C2) = + 0.5 0.5 0.5 +0.5 0.5 1 +0.5 0 +0.5 0

C2

C
0 0 1 1 = 1 0 1 0 0 0 0 1

0 0 1 1 0 1 1 0 1 0 0 1

=1

NEW D'(C2) = D'(v') =

0 1 1 0 0 0

0 0 1

1 0 D'(E) = D'(v) = 0 1 0 0

0 0 1

=1
1 0 D(C2) = D (v') = 0 0 0 1

=3
1 0 D(E) = D(v) = 0 1 0 0 0 0 1

OLD

0 1 0

=1

=3

Note that the representation for C2 and v' have changed, but in all cases the character is invariant with the similarity transformation.

Thus, all the members of a class of operations can be treated together since they are related by a similarity transformation and must have the same characters. The two 3x3 bases used to this point can be viewed as consisting of a 1x1 matrix (one basis vector not rotated into any of the others by any R: I & Z) and a 2x2 submatrix (two basis vectors rotated into one another by at least one R). Thus, the 3x3 representation has been reduced to a 1x1 and a 2x2. Indeed, the 2x2 matrix can be reduced into two 1x1 matrices. In this process, a large reducible representation is decomposed into smaller (usually 1x1 but sometimes 2x2 and 3x3) irreducible representations.

Consider the symmetry adapted linear combinations (SALC's) AC for water s-orbitals I
II III II III

A=I

B = II + III

C = II - III

A 1 0 0 I I B = 0 1 1 II = II + III C 0 1 1 III II III

In this basis, no basis vector is changed into another by a symmetry operation, i.e., this basis is symmetry adapted. Old 3x3 is now three 1x1 matrices and reducible representation S is now three irreducible representations, A, B and C. i.e., S = A + B + C I A

E C 2 '

I
II III

S = 3 1 3 1

A 1 1 1 1 B 1 1 1 1 C 1 -1 1 -1 S 3 1 3 1

A = 1 1 1 1
II III

B = 1 1 1 1
II III

C = 1 -1 1 -1

The term irreducible representation is used so frequently that it is often abbreviated as "irrep". We will also use this abbreviation throughout this lecture, irrep irreducible representation

Decomposing a reducible representation into irreps is a very important process, and a procedure to accomplish the decomposition will be described shortly.

Point Group Representations A point group representation is a basis set in which the irreducible representations are the basis vectors. The irreps form the a complete orthonormal basis for an mdimensional space, where m is the number of irreducible representations and is equal to the number of classes in the group. These considerations are summarized by the following rules. 1. The number of basis vectors or irreps (m) equals the number of classes. 2. The sum of the squares of the dimensions of the m irreps equals the order,

d
i =1

2 i

=h

expect at least one (E) > 1 for Cn (n > 2)

The character of the identity operation equals the dimension of the representation, (E) = di which is referred to as the degeneracy of the irrep. The degeneracy of most irreducible representations is 1 (nondegenerate representations are 1x1 matrices) but can sometimes be 2 or 3. No character in an irreducible representation can exceed the dimension of the representation. Thus, in non-degenenerate representations, all characters must be 1.

3. The member irreps are orthonormal, i.e., the sum of the squares of the characters in any irrep is equal to the order (row normalization), while the sum of the product of the characters over all operations in two different irreps is zero (orthogonality).

g(R) ( R)
i R

(R) = hij

ij is the Kroniker delta (0 when ij and 1 when i=j), where the sum is over all of the classes of operations, g(R) is the number of operations, R, in the class, i(R) and j(R) are the characters of the operation R in the ith and jth irreps, h is the order of the group.

4. The sum of the squares of the characters of any operation over all of the irreps times the number of operations in the class is equal to h, i.e., columns of the representation are also normalized.

g(R)
i=1

2 i

(R) = h

where m is the number of irreducible representations

5. The sum of the products of the characters of any two different operations over all of the irreps is zero, i.e., columns of the representation are also orthogonal.

(R' )
i=1 i

(R) = 0

6. The first representation is always the totally symmetric representation in which all characters are +1. 7. Any reducible representation in the point group can be expressed as a linear combination of the irreducible representations.

Lets generate the C2v point group, {C2vE, C2, , '}

C2v E C
2

v ? b e h

v' ? c f i

1 2 3 4
Rule 2
2

d1 d2 d3 d4

? a d g

2 2 2 d1 + d2 + d32 + d4 =h =4

d1 = 1
2 2 2 + d3 + d4 =3 d2

d2 = d3 = d4 = 1

Rule 6 ((1)=+1)

Use orthogonality to construct the irreducible representations

C2v E 1 1 2 3 4 1 1 1

C2 1 a d g

v 1 b e h

v' 1 c f i

Rule 3 (row 1 x row 2) 1+a+b+c=0 a + b + c = -1 a = 1; b = c = -1 (others possible)

Use orthogonality to construct the irreducible representations

C2v 1 2 3 4

E 1 1 1 1

C 2 v 1 1 d g 1 -1 e h

v' 1 -1 f i

Rule 3 (row 2 x row 3) 1+d-e-f=0 d - e - f = -1 d = f = -1; e = +1 (others possible)

Use orthogonality to construct the irreducible representations

C2v 1 2 3 4

E 1 1 1 1

C2 1 1 -1 g

v 1 -1 1 h

v' 1 -1 -1 i

Rule 3 (row 3 x row 4) 1-g+h-i=0 - g + h - i = -1 g = h = -1; i = +1

C2v 1 2 3 4

E 1 1 1 1

C2 1 1 -1 -1

v 1 -1 1 -1

v' 1 -1 -1 1

Mulliken symbols for irreps: "A"symmetric wrt rotation about principle axis ([Cn(z)] =+1) "B" irrep is antisymmetric wrt rotation about the principle axis ([Cn(z)] = -1) "E" doubly degenerate irrep (d = 2 (E) = 2) "T"triply degenerate irrep (d = 3 (E) = 3) "G" and "Hdegeneracies of 4 and 5, respectively.

In many instances there are more than one A, B, E , etc. irreps present in the point group so subscripts and superscripts are used g or u subscripts are used in point groups with centers of symmetry (i) to denote gerade (symmetric) and ungerade (antisymmetric) with respect to inversion ' and " are used to designate symmetric and antisymmetric with respect to inversion through a h plane numerical subscripts are used otherwise

For C2v:

C2v 1 2 1 2

E 1 1 1 1

C2 1 1 -1 -1

v 1 -1 1 -1

v' 1 -1 -1 1

Determination of Reducible Representations

Oxygen s-orbitals in water,

C2v E C2 v v' O(s) +1 +1 +1 +1 O(s) = a1

s-orbitals on central elements will always transform as the totally symmetric representation but are not included in character tables

Oxygen p-orbitals in water,

px C2v pz px py
p

pz C2 +1 -1 -1 -1 v(xz) +1 +1 -1 1

py v'(yz) +1 a1 -1 b1 +1 b2 1

E +1 +1 +1 3

Thus, p = a1 + b1 + b2. The px orbital is said to form the basis for the b1 representation, have b1 symmetry, or transform as b1

Translations along the x, y and z directions (x, y, z) transform in the same way as px, py and pz.
z O y x H H H O H

T(y) = 1 -1 1 -1

C2v E C2 v(xz) v'(yz) Tz +1 +1 Tx +1 -1 Ty +1 -1 trans 3 -1 +1 -1 +1 1 +1 +1 -1 1 a1 b2 b1

Thus, trans = a1 + b1 + b2

Rotation of the water molecule,

z O y x H H H

O H

R(z) = 1 1 -1 -1

C2v Rz Rx Ry
rot

E +1 +1 +1 3

C2 v(xz) v'(yz) +1 -1 -1 -1 -1 -1 +1 1 -1 +1 -1 1 a2 b2 b1

Thus, rot = a2 + b1 + b2

In most character tables, C2v has the following form:

C2v 1 2 1 2

E 1 1 1 1

C2 v(xz) v'(yz) 1 1 1 1 -1 -1 -1 -1 1 -1 -1 1

z Rz x, Ry y, Rx

x2, y2, z2 xy xz yz

The final column gives squares and binary products and represent the transformation properties of the d-orbitals.

Lets generate the C3v point group. The operations of C3v are E, 2C3, 3v (h=6, m=3) d12 + d22 + d32 = 6 d1 = d2 = 1 and d3 = 2. Since the dimensions of the irreps are the (E) and every group contains the totally symmetric irrep,

C3v 1 2 3

1E 1 1 2

2C 3 1 j m

3v 1 k n

Orthogonality of 1 with 2: (1)(1)(1) + (2)(1)(j) + (3)(1)(k) = 0 1 + 2j + 3k = 0 j = +1 and k = -1 Normalization of 3 means (1)(2)2 + 2(m2) + 3(n2) = 6 so, m = -1 and n =0.

C3v 1 2 3

1E 1 1 2

2C 3 1 1 -1

3v 1 -1 0

For C3v,

C3v 1 2

1E 1 1 2

2C 3 1 1 -1

3v 1 -1 0

The ammonia molecule (C3v point group) and the coordinate system used in the following discussion is given below (one N-H bond in the XZ plane).
z

px py pz The N-pz orbital is not changed by any of the operations of the group, i.e., it is totally symmetric and transforms as a1 However, px and py are neither symmetric nor antisymmetric with respect to the C3 or v operations, but rather go into linear combinations of one another and must therefore be considered together as components of a 2 dimensional representation. The matrices in this irreducible representation will be 2x2 and not 1x1. The character of the identity operation will then be 2 (the trace of a 2x2 matrix with 1's on the diagonal), i.e., (E)=2.

x y

A rotation through an angle 2/n can be represented by the following transformation:

x' cos( 2 / n ) sin( 2 / n ) x = y' - sin( 2 / n ) cos( 2 / n ) y

the trace of the Cn rotation matrix is 2cos(2/n) which for n=3 is 2cos(2/3) = 2(-0.5) = -1, i.e., (C3) = -1 The character for sv can be determined by the effect of reflection through any one of the three sv since they are all in the same class. Use sv(xz) which results in px px and py -py or,

x' 1 0 x = y' 0 1 y
(sv) = 0

px

py

pz

The transformation properties of the px and py orbitals are represented as,

C3v
px,py

E 2C3 2 -1

3v 0

px,py = e
The px and py orbitals are degenerate in C3v symmetry and are taken together to form a basis for the two-dimensional irreducible representation, e.

Treating rotations and binary products as before, we can represent the C3v point group as

C3v 1 2

E 1 1 2

2C3 3v 1 1 -1 1 -1 0 z Rz x2+y2; z2

(x,y);(Rx,Ry) (x2-y2,xy);(xz,yz)

The x2-y2 and xy orbitals are also degenerate as are the xz and yz orbitals

Decomposing Reducible Representations

In the determination of molecular orbital or vibrational symmetries, a reducible representation is generated from an appropriate basis set and then decomposed into its constituent irreducible representations.

1 ai = g(R) i (R) (R ) h R
ai: the # of times that ith irrep appears in the reducible representation h: the order of the group R: an operation of the group g(R): the number of operations in the class i(R): the character of the Rth operation in the ith irrep (R): the character of the Rth operation in the reducible representation

red = 7 1 1 of the C3v point group. The order of the point group is 6.

C3v 1E 2C 3v
3

C3v 2 red

1E 2C 3 1 7 1 1

3v -1 1

1 red

1 7

1 1

1 1

a(a1) = 1/6{(1)(1)(7)+(2)(1)(1)+(3)(1)(1)} = 1/6{12} = 2 a(a2) = 1/6{(1)(1)(7)+(2)(1)(1)+(3)(-1)(1)} = 1/6{6} = 1

C3v E red

1E 2 7

2C 3 3v -1 0 1 1

a(e) = 1/6{(1)(2)(7) + (2)(-1)(1) + (3)(0)(+1)} = 1/6{12} = 2

The reducible representation is decomposed as: red = 2a1 + a2 + 2e The results can be verified by adding the characters of the irreps,

C3v 2 a1 a2 2e red

1E 2 1 4 7

2C 3 2 1 -2 1

3v 2 -1 0 1

Problem I.7 Decompose the following reducible representations of the C4v point group.

C4v 1 2 3 4

E 11 6 5 4

2C4 1 0 1 -4

C2 -1 2 -3 4

2v 5 0 -1 0

2d 1 0 -1 0

The reducible representation of the Cartesian displacement vectors for water was determined earlier and is given in the following table as cart

cart(E) = 3N Here is a shortcut for generating cart for any system: cart = unshxyz = unsh[x + y + z]

C2v A1 A2 B1 B2 cart

E 1 1 1 1 9

C2 1 1 -1 -1 -1

v 1 -1 1 -1 3

'v 1 -1 -1 1 1

z Rz x, Ry y,Rx

C2v A1 A2 B1 B2 cart

E 1 1 1 1 9

C2 1 1 -1 -1 -1

v 1 -1 1 -1 3

'v 1 -1 -1 1 1

z Rz x, Ry y,Rx

Decomposition of cart yields,

a(a1) = 1/4 {(1)(1)(9) + (1)( 1)(-1) + (1)( 1)(3) + (1)( 1)(1)} = 1/4 {12} = 3 a(a2) = 1/4 {(1)(1)(9) + (1)( 1)(-1) + (1)(-1)(3) + (1)(-1)(1)} = 1/4 { 4} = 1 a(b1) = 1/4 {(1)(1)(9) + (1)(-1)(-1) + (1)( 1)(3) + (1)(-1)(1)} = 1/4 {12} = 3 a(a2) = 1/4 {(1)(1)(9) + (1)(-1)(-1) + (1)(-1)(3) + (1)( 1)(1)} = 1/4 { 8} = 2

cart = 3a1 + a2 + 3b1 + 2b2

Of these 3N degrees of freedom, three are translational, three are rotational and the remaining 3N-6 are the vibrational degrees of freedom. Thus, to get the symmetries of the vibrations, the irreducible representations of translation and rotation need only be subtracted from cart, but the irreps of rotation and translation are available from the character table. For the water molecule, vib = cart - trans - rot = {3a1 + a2 + 3b1 + 2b2} - {a1 + b1 + b2} - {a2 + b1 + b2} = 2a1 + b1
Problem I.8 Determine the symmetries of the vibrations of NH3, PtCl42- and SbF5.

Direct Products. Direct Products: The representation of the product of two representations is given by the product of the characters of the two representations. Verify that under C2v symmetry A2 B1 = B2

C2v A2 B1 A2 B1

E 1 1 1

C2 1 -1 -1

v -1 1 -1

'v -1 -1 1

As can be seen above, the characters of A2 B1 are those of the B2 irrep.

Verify that A2 B2 = B1, B2 B1= A2 Also verify that the product of any non degenerate representation with itself is totally symmetric and the product of any representation with the totally symmetric representation yields the original representation Note that,

A x B = B; while A x A = B x B = A "1" x "2" = "2; while "1" x "1" = "2" x "2" = "1 g x u = u; while g x g = u x u =g.