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Outline
1.
1.1.
1.2.
1.3.
1.4.
2.!
2.1.
2.2.
2.3.
2.4.
2.5.
2.6.
2.7.
Group representations
An intuitive approach
The great orthogonality theorem (GOT)
Theorems about irreducible representations
Basis functions
Relation between representation theory and quantum mechanics
Character tables and how to use them
Examples: symmetry of physical properties, tensor symmetries
3. !
3.1.
3.2.
3.3.
3.4.
3.5.
3.6.
4.!
Vibrations in molecules
4.1. Number and symmetry of normal modes in ! molecules
4.2. Vibronic wave functions
4.3. IR and Raman selection rules
5.!
5.1.
5.2.
5.3.
5.4.
At the end of this week, having followed the course, you should be
able to
tensorial properties of solids and derive those tensor elements which are
zero by symmetry
identify molecular orbital and electronic band degeneracies and apply the
http://symmetry.jacobs-university.de/
Structures of Neutral Au7, Au19, and Au20 Clusters in the Gas Phase
Ph. Gruene, D. M. Rayner, B. Redlich,3 A. F. G. van der Meer, J. T. Lyon, G. Meijer, A. Fielicke, Science
329, 5889 (2008)
from: Dresselhaus, Dresselhaus and Jorio, Group Theory - Application to the Physics of Condensed Matter Springer
2008 (figure given without references)
Literature
Tinkham, M Group theory and Quantum mechanics, McGraw-Hill 1964
Heine,V Group theory in Quantum Mechanics, Pergamon Press Oxford 1960
Wigner, E Gruppentheorie Vieweg, Nachdruck von 1931
Joshi, A Group Theory for Physicists, Wiley Eastern New Delhi 1977
Cotton, F. A. Chemical Applications of Group Theory, Wiley 2nd edition 1971
Burns, G. Introduction to Group Theory with Applications Academic Press 1977
Harris, D.C., Bertolucci,M.D. Symmetry and Spectroscopy Oxford University Press 1978
Inui,T, Tanabe,Y, Onodera,Y Group Theory and its Applications in Physics, Springer 1996
Vincent, A Molecular Symmetry and Group Theory, Wiley 1977
Cornwell, J.F. Group theory in Physics,Academic Press London 1984
Weyl, Hermann The Theory of Groups and Quantum Mechanics, Translated edition Dover 1950
Wilson, E. B., Decius, J.C., Cross, P.C., Molecular Vibrations Dover New York 1955
Stiefel, E., Fssler, A., Gruppentheoretische Methoden und ihre Anwendungen, Teubner Stuttgart 1979
Dresselhaus, M, Dresselhaus G., Jorio A., Group Theory - Application to the Physics of Condensed
Matter Springer 2008
Overviews in books:
Yu, P.Y., Cardona, M. Fundamentals of Semiconductors Springer 1999: Chapter 2: A Pedestrians
Guide to Group Theory,
Atkins, P., Friedmann,R. Molecular Quantum Mechanics Oxford University Press, 2005: Chapter 5:
Group Theory,
c
b
each level 2-fold
degenerate (ab = ba)
Epot
ab ac
ab
bc
bc ac
ab
bc ac
120oangle
"1 0 0% " x %
" x%
$
'$ '
$ '
0
1
0
y
Transformation matrix: $
' $ ' = $ y'
$
'$ '
$ '
#0 0 1& # z &
#z&
Symbol E
2. Reflection:
Symbol "
!
nomenclature: ", " etc, or "xy for reflection in the xy plane;
also "v for vertical, "h for horizontal, "d for dihedral
3. Rotation around an axis:
Symbol Cn
Symbol Sn
$ cos(2
! " / n) sin(2
! " / n) 0'
&
)
#sin(2
"
/
n)
cos(2
" /n) 0)
&
&
)
0
0
1(
%
#1 0 0 & " x %
! ( $!'
%
%0 1 0 ( $ y '
%
($ '
$0 0 "1' # z &
# x"&
% (
% y"(
% (
$ z"'
!
!
$ cos(2" / n) sin(2" / n) 0 ' " x %
&
)$ '
y
&#sin(2" /n) cos(2" /n) 0 ) $$ '' =
&
) z
0
0
#1( # &
%
Symbol i
" x%
$ '
$ y' =
$ '
#z&
# x"&
% (
% y"(
% (
$ z"'
# x"&
% (
% y"(
% (
$ z"'
Chirality Induction:
Adaption of a flexible, achiral object
to the handedness of a chiral object
the achiral object assumes a
chiral conformation
interact
chiral object
(#mirror image)
achiral object
C2
"xz
"yz
C2
C2
"yz
"xz
"xz
"xz
"yz
C2
"yz
"yz
"xz
C2
multiplication table
But one can also say that the closure axiom is fulfilled since any of the
products of symmetry operations transforms the object into an equivalent
conformation
2. There is a unit element E, the identity
3. There is an inverse to each element (see multiplication table)
4. Associativity holds
In the first part of the lecture course: operations that leave a point in space
fixed -> point groups
When including translations, glide planes and screw axes -> space groups
1.2.3 Multiplication tables
As seen above, group axioms can be tested by means of a
multiplication table:
Consider this set of matrices
#1 0&
%
(
$0 1'
1 # "1
%
2 $" 3
E
!
3&
(
"1 '
From Burns p. 23
#"1 0&
%
(
$ 0 1'
B
!
C
!
" 3&
1# 1
%
(
2 $" 3 "1 '
1# 1
%
2$ 3
D
!
3&
(
"1 '
a.) Subgroup
Defintion: The group S is a subgroup of the group G if all elements
of S are in G, and if S satisfies the group axioms.
It can be shown that the ratio of group orders s and g, g/s is an
integer.
b.) Conjugated elements
Let A, B, and C be members of a group G
Definition: A and B are conjugated, if they can be connected by a similarity transformation
A = X-1B X ,
H3
C3 axis normal to
paper plane
Ammonia NH3
(not planar)
H1
then B
"v
then X-1
H1
H1
"v
H1
H2
H2
H3
H2
"v
H3
H3
"v
H2
"v
A = X-1 B X
H3"v
H2
A2,
A3,...
Homomorphism: an example
Example: G1 = {+1,
-1}
C2
"v
"v
C2
"v
"v
C2
C2
"v
"v
"v
"v
"v
C2
"v
"v
"v
C2
-1 -1
-1 -1
-1 -1
-1
-1
-1
-1
-1
-1
Definition: The generators of a group are those elements from which all
elements of a group can be derived. Example: G = {C61,C62, C63, C64, C65, C66 =
E}. All elements can be derived form successive application of C61.
Chloro-bromo-fluoro-methane
H2O2
S4
Phenol Cs
Ammonia C3v
1.3.6The groups Dn
Groups contain E, Cnand n C2axes normal to Cn
1.3.7 The groups Dnd
Groups contain E, Cn, n C2axes normal to Cn, and n
mirror planes "d which bisect the angles between
the C2axes. If n is odd there is also an inversion
center.
Staggered ethane D3d
one C$ axis
b) D$h
$ "v planes
and
C2 axes
Example: N2, H2
a) Tetrahedron
d.) Dodecahedron Ih
E
12 C5 axes
20 C3 axes
15 C2 axes
i
12 S10 axes
20 S6 axes
15 " planes
96
e.) Icosahedron
truncated
icosahedron
Yes
Groups
C!v,D!h
No
Groups Cnh
Yes
Groups Cnv
No
Is there a
!v ?
Groups Sn
n C2axes
normal to Cn?
Groups T,Td,O,Oh,Ih
Yes
Yes
Groups Dnh
No
Is there a
!v ?
No
Groups Cn
Yes
Is there a
!h?
Is there a
!h?
Yes
No
axis?
Only an
improper
rotation axis?
linear ?
No
No
Groups Dn
Yes
Groups Dnd
2. Group representations
2.1 An intuitive approach
Aim: a) Represent symmetry operations by matrices
b) Find irreducible representations, i.e. matrices of lowest dimensions
Definition: A group of square matrices %(ai) is called a representation of
a point group if there is an isomorphism or a homomorphism between the
matrices %(ai) and the symmetry operations of the point group.
One way to obtain matrix representation: Cartesian
transformation matrices - weve done this before
Transformation
matrices for C3v:
"v
" 1 0 0%
$
'
$ 0 1 0'
$
'
# 0 0 1&
"(1 0 0%
$
'
$!0 1 0'
$
'
# 0 0 1&
C31
"
$
!$(
$
$$
#
"v
" (1
$
2
$( 3
$
2
$$ 0
#
( 3
2
3
(1
%
0'
'
0'
1''
&
(1
%
0'
'
0'
1''
&
C32
"v
!
" (1
$ 2
$ 3
$ 2
$$ 0
#
( 3
(1
%
0'
'
0'
1''
&
" 1
$ 2
$ 3
$ 2
$$ 0
#
3
(1
%
0'
'
0'
1''
&
2
2
matrix representations
One way to obtain matrix representation: Cartesian transformation matrices weve done this before
Transformation
E
matrices for
C3v:
"v
" 1 0 0%
$
'
$ 0 1 0'
$
'
# 0 0 1&
"(1 0 0%
$
'
$!0 1 0'
$
'
# 0 0 1&
"v
" (1
$
2
$( 3
$
2
$$ 0
#
C31
"
$
!$(
$
$$
#
( 3
2
3
(1
0
3
(1
2
2
%
0'
'
0'
1''
&
%
0'
'
0'
1''
&
C32
"!v
" (1
$ 2
$ 3
$ 2
$$ 0
#
" 1
$ 2
$ 3
$ 2
$$ 0
#
( 3
(1
0
3
(1
0
2
2
%
0'
'
0'
1''
&
%
0'
'
0'
1''
&
1 0 0
E
x1
0 1 0 * y1 = y1
0 0 1
-1
x1
z1
x1
0 -1
y1 = -y1
z1
-z1
0 -1
z1
1 0 0
x1
x1
0 1 0 * y1 = y1
0 0 -1
z1
-z1
x1
-x1
cos sin 0
-sin cos 0 * y1 = -y1
z1
z1
0
0 1
-x1
C2
x2 = x1 cos + y1 sin
y2 = -x1 sin + y1 cos
l cos !
x1,y1
r1
l sin !
cos sin 0
-sin cos 0
0
0 1
x1
*
x1
"
y1 = y1
z1
z1
-l sin(" - !)
x2,y2
l cos (" - !)
Transformation
matrices for C3v:
" (1
$
2
$( 3
$
2
$$ 0
#
" 1 0 0%
$
'
$ 0 1 0'
$
'
# 0 0 1&
"(1 0 0%
$
'
$!0 1 0'
$
'
# 0 0 1&
"
$
!$(
$
$$
#
( 3
2
3
(1
0
3
(1
2
2
%
0'
'
0'
1''
&
" (1
$ 2
$ 3
$ 2
$$ 0
#
%
0'
'
0'
1''
&
" 1
$ 2
$ 3
$ 2
$$ 0
#
( 3
(1
%
0'
'
0'
1''
&
3
(1
0
2
2
%
0'
'
0'
1''
&
12 x 12
x1
y1
z1
.
.
z4
x1
y1
z1
.
.
z4
x1,y1,z1
x4,y4,z4
H3
H1
H2
x2,y2,z2
x3,y3,z3
Apply C51 ,
counterclockwise
1
example: a
(planar) pentagon
This can be
written as
similarity
transform ->
&0
$
$0
$0
$
$0
$1
%
0
2#
5
2#
cos
5
sin
0
0
0
0
0
4#
5
4#
"sin
5
cos
1
5
1 0 0 0# & 1# & 2#
! $ ! $ !
0 1 0 0! $ 2! $ 3!
0 0 1 0! $ 3! = $ 4!
! $ ! $ !
0 0 0 1! $ 4! $ 5!
0 0 0 0 !" $% 5 !" $% 1 !"
$1
0
&
2#
0
cos
&
5
&
2#
&0 "sin
"1
C5 '= Q C5Q = &
5
&0
0
&
&&0
0
%
2
etc.
i.e. rotation by 72
There is a similarity
transformation with a matrix
Q that can transform such
matrices into block-diagonal
form (no proof here!)
'
)
)
)
0 )
)
4# )
sin
5 )
4#
cos ))
5 (
0
0
C51
C52
C53
$1
0
&
2#
&0 cos 5
&
2#
&0 "sin
"1
C5 '= Q C5Q = &
5
&0
0
&
&&0
0
%
0
2#
sin
5
2#
cos
5
0
0
0
0
0
4#
5
4#
"sin
5
cos
'
)
0 )
)
0 )
)
4# )
sin
5 )
4# )
cos )
5 (
0
" ! ii
% ji= % ij
% += % *
% += %,
% += % &1
h:
li
'
Kronecker symbol
" 1 0 0%
$
'
E = $ 0 1 0'
$
'
# 0 0 1&
$#1 0 0'
&
!)
!v = & 0 1 0)
&
)
% 0 0 1(
Blue boxes: %1
&
$
$
"v= $ '
$
$
%
2
3!
2
0
# "1
%
2
%
1
"
3
C3 = %
2
%% 0
$
' 3
'1
0
0 #!
!
0!
1 !!
"
3
"1
# "1
&
0(
% 2
( C32= 1 % 3
0(
2% 2
%% 0
1((
$
'
2
2
# 1
% 2
%
)
! v=% 3
2
%% 0
$
3
"1
0
" 3
"1
2
2
&
0(
(
0(
1((
'
&
0(
(
0(
1((
'
Red boxes: %3
"
! representations for the group C .
We will learn in a moment that there are three irreducible
3v
The third one (%2) consists of the following matrices (without proof)
+1
E
C31
C32
-1
"v
"v
"v
C 31
C 32
!v
!v
!v
-1
-1
-1
C3v
2C3
3"v
#1
#2
-1
#3
-1
traces or characters
Then, according
to the GOT:
1 &# 1 &
#"m,n
"o, p
% 2 (% 2 (
%"m,n (%"o, p ( = 0
% ... (% .. (
% n (% n (
$"m,n '$"o, p '
m,o
n,p
"li2 $ h
$#1 0 0'
&
!)
!v= & 0 1 0)
&
)
% 0 0 1(
Blue boxes: %1
"
" 1 0 0%
$
'
E = $ 0 1 0'
$
'
# 0 0 1&
&
$
$
"v= $ '
$
$
%
2
3!
2
0
# "1
%
2
%
1
"
3
C3 = %
2
%% 0
$
' 3
'1
0
0 #!
!
0!
1 !!
"
3
"1
0
2
2
# "1
&
0(
% 2
( C32= 1 % 3
0(
2% 2
%% 0
1((
$
'
# 1
% 2
%
)
! v=% 3
2
%% 0
$
3
"1
0
" 3
"1
2
2
&
0(
(
0(
1((
'
Red boxes: %3
" li2
= h
e.g. in C3v: 12+ 12+ 22= 6 = h(C3v). There is always a unique solution.
The character of the symmetry operation E (the identity), which is the
unit matrix, then gives the dimension of the irreducible
representation.
&
0(
(
0(
1((
'
nomenclature
Nomenclature:
a) Bethe: irr. reps just named
%1,%2,%3... ; (used in mathematical
treatments, for simplicity
%1,%15,%25,%25 etc.
$ " [# ( R )] " [# ( R )]
i
= h%ij
"v
example:
%1
C3v
2C3
3"v
%1
%2
-1
%3
-1
C3
%3
%
E
$ " [# ( R )] " [# ( R )]
i
= h%ij
C3v 1E 2C3
3"v
%1
%2
-1
%3
-1
example: %1, %3
[12]1 + [1(-1)]2] + [10]3 = 0
irr.reps
characters
basis functions
Example of nomenclature
" [#
(R)] =
$ a " [#(R)]
j
ajis the number of times %j appears in %red. This theorem becomes clear if we look at
the block-diagonal form of a representation matrix, and remember that the character
of a matrix does not change upon a similarity transformation.
Now we multiply
by
" # [$(R)] * :
j
% " [#
R
j$
% " [#
R
j$
% % a " [#
j
j$
j ! j'
= h" a j# jj ' = h ! a j
!
% " [#
R
j$
-> find out how many times an irreducible representation is contained in a reducible representation:
Theorem: A unique decomposition of a reducible
!
representation
into irred. reps. can be obtained from its
characters
#"11 0 0
0
%
1
0
% 0 "1 0
% 0 0 "112 "122
%
2
2
% 0 0 "21 "22
%0 0 0
0
%
0
%0 0 0
%0 0 0
0
%
0
%0 0 0
%
0
$0 0 0
0
0
0
0
0
0
0
0
0
"112
0
"122
0
0
0
0
"212 "222
0
0
0
"113
0
"123
"213 "223
"313 "323
http://symmetry.jacobs-university.de/cgi-bin/group.cgi?group=603&option=4
0&
(
0(
0(
(
0(
0(
(
0(
"133 (
(
"233 (
(
"333 '
C2 v(xz) v(xz)
A1
A2
-1
-1
B1
-1
-1
B2
-1
-1
red
Exercises
1. Molecules with a mirror plane, a center of inversion, or an improper axis of
rotation cannot be optically active (i.e. exhibit circular dichroism) those
that have not may be optically active. Which of the following molecules
may be optically active?
3.What group is obtained by adding to or deleting from each of the following groups the indicated
symmetry operation? Use the character table.
C3 plus i
S6 minus i
D3d minus S6
C3v plus i
Td plus i
S4 plus i
C3 plus S6
2C4
C2
2C2
2C2
-1
-1
-1
8
4
0
-2
0
0
0
-2
0
2
allene
a)
d)
g)
X
b)
e)
c)
h)
X
f)
k)
X
X
X
X
l)
X
X
X
X