9.

Group Theory

• Group in Physics and chemistry Point Group

• Symmetry of electronic states and vibration
• Symmetry group and rotational groups

Apr 26, 2024 | R. Saito | Solid State Physics 1

Symmetry appeared in physics and chemistry
1. Symmetry of molecule or unit cell Point Group : GP
– GP consists of rotation, mirror and inversion
– If Hamiltonian belongs to a GP, wavefunctions are
representation of GP
2. Translational symmetry Space Groups : GS
– GS consist of translation spiral Crystal structure analysis
3. Rotation of Molecule, spin Rotational Groups : GR
– GR consist of rotation (spherical symmetry)
– Rotation angle = 300, 450, 600 GP
4. N equivalent electrons or spin Symmetry Group : SN
– SN consists of N ! Permutations
–2024
Apr 26, Slater determinant,
| R. Saito many body problem
| Solid State Physics 2
 Element of A Groups
 Symmetry operation : R operation that doesn’t change shape.
- : -fold rotation : inversion : mirror
- Products of operations Definition of group
 Representation : C Objectc applied by R (wave function)
- Sign of C changes. (1D Rep.)
- changes within
Example : n dimension
n x n representation matrix
in general :
R 1  G , R 2  G  R 1R 2  G
R 1 (R 2 R 3 )  (R 1R 2 ) R 3
 Representation Space : R 1E  ER 1  R 1 , E  G
– Space unchanged by all R’s in G 1 1
R 1R 1  E, R 1  G
– Space should be closed we solve the problem in a small space
– Basis set constructing S (ex. Unit vector ) R depends on basis set

Apr 26, 2024 | R. Saito | Solid State Physics 3

 Example of Representation of Group

 Rotation in 3D Product of
(Rx = rotation along x-axis)

– Scalar variable invariant under rotation  1 D Rep.

– Vector  3D Rep. 3 X 3 rep. matrix
– Dimension of representation matrix  3 (basis x,y,z )
–
–
3 X 3 matrix
dimension is not 6 but 5
( is invariant by rotation )
– Representation matrix in rank-2 tensor.
(tensor : variables which obey rotational matrix)
 Energy Eigenvalues are degenerate Eigen function can be rep.
whose dimension is more than 2
– High degeneracy High symmetry (hidden symmetry)
Apr 26, 2024 | R. Saito | Solid State Physics 4
 Irreducible Representaion and Character
 Irreducible Representation minimum size rep.
- If we can reduce the space of rep Reducible rep.
example for 3 D rotation ( 4  3 + 1)
- Reducible rep. can be decomposed into irreducible rep.
- Eigen functions are irreducible rep.
 Character : Trace of representation matrix
- Character of irreducible (reducible) rep.
( does not depend on the basis )

- Character table : list of character for GP

Apr 26, 2024 | R. Saito | Solid State Physics 5

 How to use character table
y σh E σｈ
A1 1 1 1,x 2
z A2 1 －1 ｘ,x 3
x
• Character table : table of irreducible rep. for R and G
– Example : mirror symmetry

＝１ ＝－１
Atomic orbital

A1 Symmetric

A2 Anti- Symmetric

• Vibration of two particle

Apr 26, 2024 | R. Saito | Solid State Physics 6
 Family of Point Group
H 2O NH 3 CH 4
Td
C2 v C3 v
• G that does not contain rotation
• G that has a principle -fold axis

• Mirror with Mirror

•
• Dn with
• Symmetry of regular polyhedron C Cn
n
• N-fold Reflection symmetry S 2 Cn
Ｓ h
v v v
d
Apr 26, 2024 | R. Saito | Solid State Physics 7
 Atomic site Character χa,s

• Molecular orbital (eigenfunctions) Irred.Rep (Ir. Rep)

• How many MO`s in a Ir. Rep. ?
– Number of MO can be obtained by χas
• Definition χas number of Invariant atoms for a given rotation
– s orbital : χas Irred. Rep which belongs to {x,y,z}
– p orbitals :
– χas or are reducible rep.
– Decomposed into χ Ir. Rep See Example in next page
• Why χas gives number of MO`s ?
– Number of atoms that remain at diagonal matrix element of Rep. Matrix

Apr 26, 2024 | R. Saito | Solid State Physics 8

 Symmetry of CH4 MO`s
CH 4
• CH4 atomic orbitals C : (1S, 2S, 2Px , 2Py, 2Pz) 5
Td
H: 1S x 4  9 MO`s
• Point Groups of CH4 (Td)
Number of electron = 10, HOMO = 5th MO
Td E 6IC 4 3C 2 6 σｄ 8C 3
A1 1 1 1 1 1 s χa,s of C
A2 1 -1 1 -1 1
E 2 0 2 0 -1
T1 3 1 -1 -1 0
T2 3 -1 -1 1 0 xyz C4 ,C2
χas 4 0 0 2 1 χa,s of H
d
C3
 3 A1  2T2
Apr 26, 2024 | R. Saito | Solid State Physics 9
 C4 , C2
• 5 MO`s 3A1+2T2
– MO-1 A1 C 1s Orbital d
– MO-2 A1 C 2s + H 1s orbitals C3
– MO-3-5 T2 C (2s, 2p) + H 1s
(HOMO) (3-fold deg.) CH4 full charge density
• MO`s are similar to AO`s
– MO-1, MO-2, MO-3-5 are similar to 1s, 2s, 2p, respectively
– 4 sp3 bonding is not correct images
– HOMO of CH4 are 3-fold deg. stable molecule
• Stability of a molecule HOMO-LUMO gap HOMO of CH4

– Charge distribution is similar to a sphere a quasi atom

• Reduction of symmetry from GR Td
(rot. G) (Point G)

Space-filling model vs charge density

Apr 26, 2024 | R. Saito | Solid State Physics 10
 Optical Absorption and Emission
B
 
• Symmetry of Matrix and Wavefunction A
– even function in space
– (Full symmetric)

– Eigen energy can be obtained in Irred.Rep. Space

• Optical absorption and emission ∝ Dipole moment vector

• Ex. CH4 MO`s XPS UPS

T2
– T2 A1 allowed optical transition A1 LUMO
contains A1 T2 HOM

– O occupied (T2) unoccupied (A1) A1 O

– X occupied (A1) unoccupied (A1) A1 C1s

– X occupied (T2) unoccupied (T2)
Apr 26, 2024 | R. Saito | Solid State Physics 11
 Symmetry of Molecular Vibration
For mirror σ
σCn  - Cn

• Calculate number of normal mode by χa,s

• Number of atoms 3 N freedom
– decompose
– Among 3N, 3 is translation ( )
– Among 3N, 3 is rotation ( χ (axial vector) )
3N – 6 Freedom
(3N -5 for axial molecule ) σCn  - Cn
• 3N – 6 Freedom Normal mode (Irred. Rep.)
Among them
– χ (2nd rank ) Raman active Mode
• etc Polarization Tensor α
– χ (x,y,z) Infra Red Active Mode
Apr 26, 2024 | R. Saito | Solid State Physics 12
 Vibration of CH4 Molecule
⇒ Decompose 3N-6 freedom of vibration ⇒ Normal mode

• Ex. CH4 N = 5 , freedom of vibration 3N – 6 = 9 (Normal Modes)

• Point Group (g=24)
Td E 6IC 4 3C 2 6 σｄ 8C 3
A1 1 1 1 1 1 s
A2 1 -1 1 -1 1
E 2 0 2 0 -1
T1 3 1 -1 -1 0 Irreducible rep. for rotation
T2 3 -1 -1 1 0 xyz Irreducible rep. for translation
χas 5 1 1 3 2 for CH4 .
χv ib 15 -1 -1 3 0 Reducible character for
vibration C ,C4 2

d
Raman Active : 3
C3
IR Active : 2
Apr 26, 2024 | R. Saito | Solid State Physics 13
 IR Active and Raman Active

• Point group without having inversion (such as )

– Same Irred. rep. for IR and Raman is possible

• For Point group with

– Each Irred. rep. is either even (g) or odd (u) for I
– (g : gerade, u : ungerade)
–
– IR and Raman active modes belong to different Ired.rep.
– This is used for checking the existence of

Apr 26, 2024 | R. Saito | Solid State Physics 14

 Rotation Motion of CH4 Molecule

• Molecule is rotating as a rigid molecule (Approx.)

– Moment of Inertia (around center of mass)
– Quantum angular momentum
– degeneracy for a given state
(Spherical rotor ⇒ degeneracy)
• 4 H atoms are equivalent
– Wave function for rotation motion ⇒ Symmetric for
exchanging any of 2 H atoms
– symmetry only for rotational wave function
– Red. Character of rotation ⇒ decomposition by
– Representation of rotational group ⇒ (for a fixed axis)

Apr 26, 2024 | R. Saito | Solid State Physics 15

 Decomposition of YLM

• Character is invariant for changing axis ⇒ z axis

– L is invariant under changing axis
• Eigenfunction for

• Rotation by around z-axis : diagonal matrix

• Example Mirror Inversion

off diagonal
element

Only Survives
Apr 26, 2024 | R. Saito | Solid State Physics 16
 Decomposition of YLM in Td

For each L, reducible rep. is calculated ⇒ decomposition

Td E 6IC 4 3C 2 6 σｄ 8C 3
A1 1 1 1 1 1 s L=0
A2 1 -1 1 -1 1
E 2 0 2 0 -1
T1 3 1 -1 -1 0
T2 3 -1 -1 1 0 xyz L=1
χＬ＝２ 5 -1 1 1 -1 L=2
χＬ＝３ 7 1 -1 1 1 L=3
Shottky abnormal
in specific heat

Rotation of CH4 L = 0,3,… (L = 1,2 are forbidden)

Rotation of C60 L = 0,6,… (L = 1,…5 are forbidden)

Degeneracy for of CH4 is 1 ⇒ a large isotope effect for CH3 D(C3V),CH2D2(C2V),etc

Apr 26, 2024 | R. Saito | Solid State Physics 17

 Projection Operator

• We know how many Irred.Rep’s for each

– How to make a Molecule Orbital that belongs to
• When two MO’s belong to
• Projection Operator
• Ex.: A 2 atom molecule (H2) (g=2,d=1)
σh E σｈ
A1 1 1 1,x 2
A2 1 －1 ｘ,x 3
• For E,T Irred.Rep
⇒ We can use ij element rep. matrix Same in the case of vibration

Apr 26, 2024 | R. Saito | Solid State Physics 18

 Summary

• Definition of Group, Representation, Rep.Matrix,

C ,C
Character 4 2

• Use of Symmetry by character table  d

– Number of Irred.Rep in MO,Vib,Rot C3

– Selection Rule of optical absorption and emission

– Raman and IR active modes
• Decomposition of Rotational group to Point group
– YLM Td (Rotational mode selection)
• Projection operator ⇒ Generation of MO in
T2

Apr 26, 2024 | R. Saito | Solid State Physics 19

 Problems
• Select a molecule and examine the following facts
– Point Group, Character Table, Number of MO in
– Selection rule for optical absorption, Raman (IR) active
modes
– Compare with Gaussian results
• Select any subjects of Group and discuss
– Space Group (definition, How to use)
– Symmetry Group
• Learn following keywords and explain how to use
– Irreducible tensor, spherical rotors, Young’s diagram,
Dipole selection rule

Apr 26, 2024 | R. Saito | Solid State Physics 20