CHE4114 – Advanced Inorganic

Chemistry

Assessment : Semester-end examination

3 hour theory paper
All compulsory six questions

1
 Molecular symmetry and Group theory
CHE 4114
Atkins - Physical Chemistry

Ogden – Introduction to Molecular Symmetry (Oxford

Chemistry Primer)
Cotton – Chemical Applications of Group Theory

Davidson – Group Theory for Chemists

Kettle – Symmetry and Structure

Shriver, Atkins and Langford – Inorganic Chemistry

2
 What do symmetry and shapes have to do
with chemistry?
Remember that the way waves are allowed to travel through 2D
space depends on the energy of the waves and the shapes of
the plane

The same phenomena happens in 3D space, thus the shape

of molecules dictates the electronic and other properties of
molecules

Symmetry Operation: Moves an object into a new orientation

that is indistinguishable from its original appearance

Symmetry Element: point line or plane with respect to which a

symmetry operation is carried out
3
1. Identity Symbol: E
This means do nothing. It represents the lowest
order of symmetry. All molecules posses the identity
symmetry element.

2. Proper rotation axis Symbol: Cn , n = 2, 3, 4, 5,

An axis about which the molecule may be rotated
2πm/n radians. The values of m are 1, 2,. ,n. A two-
fold rotation axis means rotation by π radians, or 180
. A three-fold axis means rotation by 120 , etc. A
molecule may have more than one order of axis; that
axis with the largest value of n (highest order) is
called the principal rotation axis.

4
3. Mirror planes Symbol: σh, σv, σd
σh - horizontal mirror plane is a plane of reflection
normal to the principle rotation axis.
σv - vertical mirror plane is a plane of reflection
containing the principle rotation axis.
σd - dihedral mirror plane is a plane of reflection
containing the principle rotation axis which also
bisects two adjacent C2 axes perpendicular to the
principle rotation axis

4. Center of symmetry : i
Also called an inversion, it means simply that: invert
the position of all the atoms with respect to the
center of symmetry of the molecule. In coordinate
language, this means converting x, y, z to -x, -y, -z. 5
The Improper Rotation Operation (Sn)
• The improper rotation operation Sn is also known as
the rotation‐reflection operation and is a compound
operation.
• Rotation‐reflection consists of a proper rotation
followed by reflection in a plane
perpendicular to the axis of rotation.

• n refers to the improper rotation by 2π / n = 360° / n.

• Sn exists if the movements Cn followed by σh (or vice
versa) bring the object to an equivalent position.
• If both Cn and σh exist, then Sn must exist.
e.g., S4 collinear with C4 in planar MX4.
• Neither Cn nor σh need exist for Sn to exist.
e.g., S4 collinear with C2 in tetrahedral MX4 6
 Some Vocabulary
in 3D space there are three types of mirrors
sh = perpendicular to principle axis Cn (highest n)
sv = contains entire principle axis Cn (highest n)
sd = same as sv but contains fewer poins (atoms)

sh = bisects the 2 sd ‘s contain C4 axis and

2 sv ‘s contain C4 axis and three only one Pt atom
Principle (C4 ) axis atoms each
Contains all five atoms (bisecting Cl’s)
(Pt and both Cl’s)

7
 Improper Rotations, Sn
Sn = rotate by 360o/n then reflect into plane
perpendicular to rotation axis ( = Cn*sh)
**A molecule with an Sn axis is not chiral**
example: S4 axis
Top View (2D)
1 2 3
key o S S S
o Out of plane 4 x 4 4
x
x In-plane o
4
E=S 4

Perspective
View (3D)
An S4 axis demarcates the points of a tetrahedron
S1 axis is a mirror plane
S2 axis= inversion center = i
rotate 180o reflect ⊥ to rotation axis
converts (x,y,z) to (-x, -y, -z)
C2 sH

8
 Special Symmetries
Low symmetry

C1 No symmetry elements other than

identity
Ci Only inversion View down C-C bond

Cs
Only one mirror

High symmetry
K Spherical
Infinite # of mirrors and rotation
axes and C∞‟s
9
 High symmetry
D∞h Linear, Symmetric C2
One C∞, one sh C∞ F F
sv’s
Infinite sv’s, C2’s C2
C∞ sh

C∞v Linear, Asymmetric C∞ C∞

One C∞
Infinite sv’s,
NO sh or C2’s H F

Td Tetrahedral (24 symmetry operations)

But no inversion center!
C3 S4
Rotations:

C2

10
 Oh Octahedral (48 symmetry operations) (cube or
octahedron) View down C3 and S6
showing sd’s

sh
sd
C4*i = S4 (x3)
Proper rotation axes (only one of
each shown)
C3*i= S6 (x4)
( an inversion center is located
where all cross) C2*i= s (x6)
Ih Icosahedral (120 symmetry operations)
(rare) Examples: C60, (B12H12)2- Six C5
Ten C3
( an Fifteen C2 is located
inversion center
where all cross)
C5*i = S10 (x6)
C3*i= S6 (x10)
C2*i= s (x15) 11
 Point Groups
a set of symmetry elements operating on a system in which at
least one point is not translated under any operation

Special Group? no Special Group

start High symmetry? low symmetry?
T, Th, Td, O, Oh, I, Ih C1 Ci, Cs
Multiple high-order axes no
C∞v, D∞h
Linear
Only S2n?
Dnh S4 , S 6 , S 8 …
sh no
yes Find highest Cn
sd D - group
No s Any ┴ Cn’s?
Dnd no
Dn C - group
No s sv sh
Cn Cnv Cnh
12
 Point Groups and Properties
Dipole Moments
Only molecules with point groups:
C1  Cn, Cs, and Cnv have dipole moments
trans-[PtBr2I2]2- cis-[PtBr2I2]2-

Point Group: D2h Point Group: C2v

Polar? No Polar? Yes
fac-[WBr3I3] mer-[WBr3I3]

Point Group: C3v Point Group: C2v

Polar? Yes Polar? Yes
Geometric isomers:
Two or more molecules or ions with same empirical formula but
different spatial arrangement of bonded atoms 13
 Point Groups and Properties
Chirality
Only molecules with point groups:
C1, C2  Cn, D2  Dn are chiral
Chiral molecules cannot have an Sn axis:
S1 = s and S2 = i:

C2

Point Group: C2 Chiral? Yes Polar? Yes

Optical isomers: Chiral compound and its non-
superimposable mirror image
Place one ring in the back, see
how other ring is connected from
top position to front:
Top left front = L Top right front = D
14
 Foundations of Group Theory
Group: complete set of symmetry elements inter-related by
certain mathematical rules
Four shared properties of groups:
[1] Each group contains and identity element that commutes all other
members and leaves them unchanged
A·E = E·A = A

Multiplication in group theory is different than arithmetic

In group theory perform symmetry element on right first
“A·E” translated means do E followed by A
Example: s·C 13 s
C 13 s
Do this 1st
s 1
s C 3
NOT this 1st
You might end up somewhere you are
15
not supposed to go
 Four Shared Properties of Groups, Cont’d.
[2] Each symmetry operation has an inverse that when combined with
the original symmetry element yields the identity

A·(A)-1 = E thus, if (A)-1 = B then A·B=E

Some symmetry elements are their own inverse
E·E = E
do nothing followed by do nothing = do nothing
C2·C2 = E
180o rotation followed by a 180o rotation = 360o rotation = do nothing

In general for rotations, inverse of C m is C (n-m)

n n
(4-1)
(C1)-1 = C 4 =C3
4 4

C 3 ·C 1 = E C 14
4 4 3 16
C 4
 Four Shared Properties of Groups, Cont’d.
[3] The product of any two symmetry operations gives rise to another
or the same member of a group (closure requirement)

C 3 C 14
2 1 3 4
C 4
·C 4
= C 4
2
C 4
Example 2, in C3v point group:
sv ”
sv ·C 13 =? C 13 sv ·C 13 = sv’
sv ’
sv
[4] The Associative Law holds: A(BC) = (AB)C
perform product in parentheses first
Example in C3v 1 (s s ’)
C 3 v v = (C 13 sv)sv’
sv ”
C 1 sv ”
3
sv ’ 2 2
sv C 3
= C 3
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 Developing members of the C3 Point group
In order to form a group the above four conditions MUST be met

[1] Each group contains and identity element, E

[3] if C31 is a member, then products must be
members
E·E = E C31·C31 = C32
E·C31 = C31 New member!
Does this new member generate any more members?
Found inverse C32·C31 = E NO new
members! C32·C32 = C31 members
Property
[2]
Does the Associative Law hold? Property [4]
(build a multiplication table to evaluate this)

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Group Multiplication Tables
Does the association law hold?
2nd operation First operation
C3 E C 13 C 23
E E C 13 C 23
C 13 C 13 C 23 E
C 23 C 23 E C 13
1 1 1 1 2
C 3
(C 3
· C 23 ) = (C 3
·C 3
) C 3
3 2
C = E C 3
3
1 1
C 3 = C 3

Yes, associative law holds,

all four criteria are met, this is a complete group

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 Construction of Character Tables
There are several methods for converting group multiplication tables
into numbers useful for later manipulations
Method (1) Brute Force Substitution
-Substitute numbers for each character ci(R) ,
& see if arithmetically and group mult. valid
C2v E C2 sv sv ’
E E C2 sv sv ’
C2 C2 E sv ’ sv
sv sv sv ’ E C2
sv ’ sv ’ sv C2 E

Gi,’s = irreducible representations: non-trivial solutions that cannot be

simplified
If each character were zero, this would be a trivial case

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 Construction of Character Tables
Checking the Projection Operator Method
Try G2: c(E) = c(sv) = 1 & c(C2) = c(sv’) = -1
1= -1= 1= -1= 1= -1= 1= -1=
C2v E C2 sv sv ’ C2v E C2 sv sv ’
1= E E C2 sv sv ’ 1= E +1 -1 +1 -1
-1= C2 C2 E sv ’ sv math -1= C2 -1 +1 -1 +1
1= sv sv sv ’ E C2 1= sv +1 -1 +1 -1
-1= sv ’ sv ’ sv C2 E -1= sv’ -1 +1 -1 +1
Check that the original group/# assignments hold:
C2·sv = sv’ Mathematically correct
Original assignment c(sv’) = -1
(-1)·(1) = (-1) NOW holds! Try others…
Works easily for simple point groups like this
- difficult for multidimensional representations.
Example: almost impossible to do for C3v
unless use f-orbitals
for C4v you would need g- orbitals and math
tricks… 21
 Construction of Character Tables
Method (2) Projection Operator Method
See how nodal properties of various orbitals change under various
operations.
(a) Assign right handed axes
(b) Usually highest Cn = z-axis
(c) If lobes stay same = +1
if lobes change sign = -1
C2v E C2(z) sv(xz) sv(yz)
z

x y +1 +1 +1 +1 Same = G1

different = G2
+1 -1 +1 -1
Another
+1 -1 -1 +1 different = G3
x the last
different = G4
y +1 +1 -1 -1
22
 Properties of groups
1. Total # of symmetry operations = order of the
group (h)

2. Symmetry operations are arranged in classes

C2v point groups, 4 classes.

3. # of irreducible representation = class ( rows = columns)

4. The sum of the squares of the dimensions ( under E) = h

5. Sum of squares of characters multiplied by the # of operations = h

6. Irreducible representations are orthogonal to each other.

7. A totally symmetric representation is included

In all groups, with character of 1 for all operations. 23
 Construction of Character Tables
Practice on a real easy example
C2 E C2 # classes = 2
E E C2 Each element is in a class with itself
C2 C 2 E 2 irreducible rep’s

C2 E C2 Totally C2 E C2
G1 symmetric G1 1 1
G2 Rep. exists G2

C2 E C2 dimensionality
orthogonality G1 1 1 S li = h
2

S g(R)[ci(R)][cj(R)] = 0 G2 1 l12 + l22 = 2

12 + l22 = 2
g(E)[c1(E)]*[c2(E)] + g(C2)[c1(C2)]*[c2(C2)] = 0
l22 = 1
1*1*1 +1*1*[c2(C2)] = 0
l2 = ±1
1 + [c2(C2)] = 0 C2 E C2 but c(E) is always
[c2(C2)] = -1 G1 1 1 positive
G2 1 -1 l2 = +1
24
 Construction of Character Tables
Example of C3v
# classes:

# members = 3
(sv1 , sv2, and sv3)
# members = 2 (C31 and
C32)
C3v E 2C3 3sv
G1
G2 Three classes
G3 = 3 irred. reps

25
 Construction of Character Tables
Example of C3v

C3v E 2C3 3sv 3 classes=3 irred. reps

G1 1 1 1 (totally symmetric rep. exists) G1 =
G2 1 +1 +1 +1
G3 2 dimensionality
S li2 = h
Hopefully it is obvious that one of l12 + l22 + l32 = 1+2+3
these must be 1 while the other is 2 12 + l22 + l32 = 6
l22 + l32 = 5
The bigger l #’s are lower in the table
orthogonality G1*G2: finding characters for G2
g(E)*[c1(E)]*[c2(E)]+g(C3)*[c1(C3)]*[c2(C3)]+g(sv)*[c1(sv)]*[c2(sv)]=0
1*1*1 +2*1*[c2(C3)] + 3*1*[c2(sv)] = 0
C3v E 2C3 3sv 1 +2*[c2(C3)] + 3*[c2(sv)] = 0
G1 1 1 1 c2(C3) must be 1 and c2(sv)
G2 1 1 -1 is -1
G3 2 26
 Construction of Character Tables
Example of C3v
C3v E 2C3 3sv
G1 1 1 1 finding characters for G3
G2 1 1 -1
G3 2 (a) G1*G3= 0
g(E)*[c1(E)]*[c3(E)]+g(C3)*[c1(C3)]*[c3(C3)]+g(sv)*[c1(sv)]*[c3(sv)]=0
1*1*2 +2*1*[c3(C3)] + 3*1*[c3(sv)] = 0
Multiple possibilities:
(-1, 0) or (2, -2) or
2[c3(C3)] + 3[c3(sv)] = -2
(0, -2/3), etc… (b) G2*G3= 0
g(E)*[c2(E)]*[c3(E)]+g(C3)*[c2(C3)]*[c3(C3)]+g(sv)*[c2(sv)]*[c3(sv)]=0
1*1*2 +2*1*[c3(C3)] + 3*(-1)*[c3(sv)] = 0
2[c3(C3)] - 3[c3(sv)] = -2
2[c3(C3)] + 3[c3(sv)] = -2 C3v E 2C3 3sv
2[c3(C3)] - 3[c3(sv)] = -2 G1 1 1 1
4[c3(C3)] = -4 G2 1 1 -1
[c3(C3)] = -1  [c3(sv)] = 0 G3 2 -1 0
27
 convert Gn’s to Mulliken Symbols

D4 E 2C4 C 2 2C2 2C2‟

4
A1 G1 1 1 1 1 1 z
A2 G2 1 1 1 -1 -1 xy
B2 G3 1 -1 1 -1 1 x2-y2 xyz
B1 G4 1 -1 1 1 -1 (x,y)
E G5 2 0 -2 0 0
Mulliken
c(E) Symbol Subscripts:
1 A Symmetric (+1) to 1 = symm (+1) for
highest Cn C2 ┴ to Cn of D group
1 B or sv of C group
asymmetric (-1)
2 E 2 = asymm (-1) for
3 T C2 ┴ to Cn of D group
4 G or sv of C group
g = gerade
5 H
symm (+1) to inversion
Superscripts:
Single prime „ = symm (+1) to sh u = ungerade
Double prime “ = asymm (-1) to sh = asymm (-1) to i 28
 Character Tables
C2v E C2 sv(xz) sv‟(yz)
A1 1 1 1 1 z
A2 1 1 -1 -1 Rz
B1 1 -1 1 -1 x Ry
B2 1 -1 -1 1 y Rx
Gxyz 3 -1 1 1

Add together characters of

irreducible reps spanning x, y & z
(A1+B1+B2)
= translational elements

this is a REDUCIBLE representation

Can be decomposed to simpler irreducible representations

29
 Reducing a Reducible Representation
a
C2v E C2 sv(xz) sv‟(yz)
A1 b 1 1 1 1 z
A2 1 1 -1 -1 Rz
B1 1 -1 1 -1 x Ry
B2 1 -1 -1 1 y Rx Character of
Gxyz 3 -1 1 1 symmetry operation
c
# times irred. Rep. is “R” in reducible
found in reducible representation
a b
rep.
ai = (1/h) SR (gR)[ci(R)][cj(R)]
c
Order = sum of Coefficient of Character of
coefficients in front of symmetry
symmetry operations operation symmetry oper. “R” in
irred. rep
For C2v: h = 1+1+1+1 = 4
30
 Reducing a Reducible Representation
a
C2v E C2 sv(xz) sv‟(yz)
A1 b1 1 1 1 z
A2 1 1 -1 -1 Rz
B1 1 -1 1 -1 x Ry
B2 1 -1 -1 1 y Rx
Gxyz 3 -1 1 1
c
ai = (1/h) SR (gR)[ci(R)][cj(R)]
A1: a1 = (1/4) [ (1·1·3)+(1·1·-1)+(1·1·1)+(1·1·1)]
= (1/4) [ (3)+(-1)+(1)+(1)] = (1/4) [4]
=1
A2: a2 = (1/4) [ (1·1·3)+(1·1·-1)+(1·-1·1)+(1·-1·1)]
= (1/4) [ (3)+(-1)+(-1)+(-1)] = (1/4) [0]
=0
Of course b1 = b2 = 1 because we added these together with
A1 to get Gxyz 31
 IR and Raman Spectroscopy
measure vibrational motions of atoms in molecules (bond
stretching and bending)
Bond Stretching Analysis:
(1)Assign point group and right handed axes
(2)Assign vectors to bonds under consideration
(3)Apply each symmetry operation of point group
-if vector moves = 0; if stays same = +1
(4) Reduce the resulting reducible representation

Example: H2O
C2v E C2 sv(xz) sv‟(yz)
z A1 1 1 1 1 z x2,y2,z2
x A2 1 1 -1 -1 Rz xy
y B1 1 -1 1 -1 x Ry xz
O
H H B2 1 -1 -1 1 y Rx yz
Gstr 2 0 2 0 32
 IR and Raman Spectroscopy
measure vibrational motions of atoms in molecules (bond
stretching and bending)

Selection rule: A molecular vibration is

IR active = change in dipole moment

(irred. rep acts as x, y, or z)
Raman active = changes polarizability
(acts like 2nd order term: x2, y2, z2, xy, xz, or yz)

Example: H2O C2v E C2 sv(xz) sv‟(yz)

z A1 1 1 1 1 z x2,y2,z2
x A2 1 1 -1 -1 Rz xy
y B1 1 -1 1 -1 x Ry xz
O
H H B2 1 -1 -1 1 y Rx yz
Gstr 2 0 2 0 33
 Bond Stretching
Example: H2O C2v E C2 sv(xz) sv‟(yz)
z A1 1 1 1 1 z x2,y2,z2
x y A2 1 1 -1 -1 Rz xy
O B1 1 -1 1 -1 x Ry xz
H H B2 1 -1 -1 1 y Rx yz
Reduce: Gstr 2 0 2 0
need two of the above irred. reps since Gstr is 2D and all irred. reps
only 1D. Could do by inspection, but we will practice the systematic
method
A1: a1 = (1/4) [ (1·1·2)+(1·1·0)+(1·1·2)+(1·1·0)]
= (1/4) [ (2)+(0)+(2)+(0)] = (1/4) [4] =1
A2: a2 = (1/4) [ (1·1·2)+(1·1·0)+(1·-1·2)+(1·-1·0)]
= (1/4) [ (2)+(0)+(-2)+(0)] = (1/4) [0] =0
B1: b1 = (1/4) [ (1·1·2)+(1·-1·0)+(1·1·2)+(1·-1·0)]
= (1/4) [ (2)+(0)+(2)+(0)] = (1/4) [4] =1
Gstr = A1 + B1
IR IR
R R 34
 Visualizing Bond Stretches
The Pictorial “projection operator” Approach
Use pure rotation sub-group Cn
or expanded form of Dn subgroup
(this is not strictly necessary in all cases (such as C2v) but it is in others, and this procedure
usually simplifies matters)

(a) See how a bond vector transforms under each symmetry

element
(b) Multiply by character of irreducible rep
where a (-1) will swap ends of vector
(c) Add together

The pure rotational subgroup of C2v is C2

35
 Visualizing Bond Stretches
The Pictorial “projection operator” Approach
Use pure rotation sub-group Cn
or expanded form of Dn subgroup

The pure rotational subgroup of C2v is C2

O C2 E C2
H H A 1 1 z
Gstr = A1 + B1 B 1 -1
x y

A: 1* + 1* = O Symmetric
H H stretch

B: 1* + -1*
O Asymmetric
+ = H H stretch 36
 Visualizing Bond Stretches
The Mathematic Approach
Assign DSn to each vector, see how DSn transforms
C2 E C2
DS1 DS2 A z
O 1 1
H H B 1 -1 x y
Gstr = A1 + B1 DS1 DS1 DS2

A: 1* DS1 + 1* DS2 = DS1 + DS2 Symmetric stretch

Both bonds either increase or decrease in length at same time

B: 1* DS1 + -1* DS2 = DS1 - DS2 Asymmetric stretch

One bond increases while other decreases in length

37
 Visualizing Bond Stretches
The Mathematic Approach

As a note, for the above analysis we could have used the C2v point group directly because each
symmetry element is in its own class, (in other higher symmetry point groups we would have to
use expanded forms) but the analysis gets redundant and tedious….

Z
C2v E C2 sv(xz) sv’ (yz)
O X y (toward you)

H H

Symmetric stretch
A1: 1* + 1* + 1* + 1* =2 O
H H

B1: 1* + -1* + 1* + -1*

+ + + Asymmetric stretch
=2 O
H H 38
 IR Spectroscopy
Find normal stretching modes for NH3
Ds C3v E 2C3 3sv
Ds1 N 3
A1 1 1 1
H
H Ds2 A2 1 1 -1
H E 2 -1 0 reduce
Gstr 3 0 1 A1 + E
To visualize stretching modes
 projection operator in C3 subgroup
C3 E C31 C32
Ds1 Ds1 Ds2 Ds3
The „A‟ rep is easy:
A 1 1 1
1 e e* 1*Ds1+1*Ds2+1*Ds3
E (totally symmetric stretch)
1 e* e 1 Ds N Ds
3
H
The „E‟ representation, is not so H 2Ds
H
easy All bonds lengthen or all shorten
Need to convert imaginary e to at same time
real #’s 39
 Imaginary-Real Conversion
C3 E C31 C32
Ds1 Ds1 Ds2 Ds3
A 1 1 1
Make linear (a) 1 e e*
E(b) 1 e* e
combinations
e = e2pi/3
= cos (2p/3) + isin (2p/3)
E(a+b) 2 (e+e*) (e*+e) = (-1/2) + isin (2p/3)
(a-b) 0 (e-e*) (e*-e)
e* = cos (2p/3) - isin (2p/3)
Convert using Euler‟s = (-1/2) - isin (2p/3)
relations (e+e*) = (e*+e) = -1
(e-e*) = 0 + 2isin (2p/3)
E(a+b) 2 (-1) (-1) = 1.732i
(a-b) 0 (1.732i) (-1.732i) (e*-e) = 0 - 2isin (2p/3)
= -1.732i
Divide last rep by
2 -1 -1
1.732i E(a+b)
(a-b) 0 1 -1
40
 Imaginary-Real Conversion
E C31
C3 C32
Ds1 N Ds3 Ds1
Ds1 Ds2 Ds3
H
H Ds2 A
1 1 1
H 2 -1 -1 (a+b)
E 0 1 -1 (a-b)/1.732i
So, projection operators become:
For E(a+b) : 2 Ds1 –Ds2 – Ds3 N Ds3 H
Ds1
One bond gets stretches twice the amount the others Ds2
shorten and vice versa H H

For E(a-b) : Ds2 – Ds3

One bond gets stretches while another shortens, the N Ds3 H
third doesn’t move H Ds2
H

41
 Total vibrational motion
normal modes of vibration
(stretching and bending):

(1) Find stretching Gstr, as before

(2) Find total 3D motion G3D

3 degrees of freedom*n atoms c(E) = 3n

(3) Assign each atom its own three axes (a,b,c)

- apply symmetry operations
- see how vectors transform

-If vector translates (all points move)  0

-If vector stays the same  +1
-If vector rotates (one point is same)  cos no
42
 Total vibrational motion
normal modes of vibration
(stretching and bending):

(4) Eliminate translations (Gxyz),

eliminate rotations (RxRyRz = Grot),
and stretches Gstr to give bending Gbend

(5) Use projection operators to illustrate bending

Gbend

43
 Normal modes of vibration
(stretching and bending):
Example for NH3
Position vector axes for convenience along bonds
: or symmetry elements H
c
N c a
b
H a b H N
H
H
H
C3v E 2C3 3sv
A1 1 1 1 z
Gxyz = A1 + E
A2 1 1 -1 Rz
E 2 -1 0 (x,y) (Rx,Ry) Grot = A2 + E
Gstr 3 0 1 Gstr = A1 + E
reduce

44
 Normal modes of vibration
(stretching and bending):
Total 3D motion G3D c H
c a
b
For symm. oper., E: a b H N
[c(E) = 3n]
4 atoms *3 vectors = 12 H

For symm oper., C3:

All H atoms translate, their vectors = 0
For N: vector a stays same = +1
vector b rotates 120o, cos 120o = -1/2
vector c rotates 120o; cos 120o = -1/2

c(C3) = (9*0 + 1 – ½ – ½) = 0

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 Normal modes of vibration
(stretching and bending):
Total 3D motion G3D
b b
a c
c a
H sv
H N
-b -b
H

For symm oper., sv: +4 – 2 + 6*0 = +2

Vectors a and c on N and on H remain

same = +4

Vectors b reflect into –b, ~ 180o rotation = cos 180o = -1 each; total -2

These six circled vectors translate = 0

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 Normal modes of vibration
(stretching and bending):
C3v E 2C3 3sv
A1 1 1 1 z
Gxyz = A1 + E
A2 1 1 -1 Rz
E 2 -1 0 (x,y) (Rx,Ry) Grot = A2 + E
Gstr 3 0 1 Gstr = A1 + E
reduce
G3D 12 0 2 G3D = 3A1 + A2 + 4E

G3D = 3A1 + A2 + 4E
-Gxyz = -A1 -E
-Grot = -A2 -E
-Gstr = -A1 -E
Gbend = A1 + E

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 Normal modes of bending
To visualize bending modes
use
1
projection
2
operators in C3 subgroup
C3 E C3 C3
Db1 Db1 Db2 Db3 Gbend = A1 + E H
Db3
A 1 1 1 H N Db1
2 -1 -1 (a+b) Db2
E 0 1 -1 (a-b)/1.732i H
A: 1*Db1+1*Db2+1*Db3 = Db1+Db2+Db3
(all bond angles increase or all decrease simultaneously)
Occurs via flattening or N H N
pyramidalization H H or H H
H
E(a+b): 2*Db1-1*Db2-1*Db3 = 2Db1-Db2-Db3
Gets 2x as large as others get smallerl
Or
Gets 2x as small as others get larger Db3 H
H N Db1
Db2
H
Scissor motion
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 Normal modes of bending
To visualize bending modes
use projection operators in C3 subgroup
C3 E C31 C32 Gbend = A1 + E
Db1 Db1 Db2 Db3 H
Db3
A 1 1 1 H N Db1
2 -1 -1 (a+b) Db2
E 0 1 -1 (a-b)/1.732i H
N
A: 1*Db1+1*Db2+1*Db3 = Db1+Db2+Db3 H H
H or N H
H H
E(a+b): 2*Db1-1*Db2-1*Db3 = 2Db1-Db2-Db3
Db3 H
H N Db1
Db2
H

E(a-b): 0*Db1+1*Db2-1*Db3 = Db2-Db3

Db1 unaffected by opposing motions of Db3 H
other two H N Db1
Db2
wagging motion H
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