CHEM400/740: Quantum Mechanics in Chemistry

Chapter#02

Marcel Nooijen

Contents
1 Review Session 2

2 Full Configuration Interaction 3

2.1 Orders of the orbitals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2 Two­electron Interaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3 Excited Determinants and Full Configuration Intereaction . . . . . . . . . . . . . . . . 6

3 Hartree­Fock Approximation 7
3.1 Self­consistent Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

4 Symmetry in Quantum Mechanics 9

4.1 General Principal of Symmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.2 Group . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.3 Example of Groups in Physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4.4 Consequences of Symmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.4.1 Example: Particle on a Ring . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.4.2 Consequences of Symmetry: Multiplet . . . . . . . . . . . . . . . . . . . . . 16
4.4.3 Consequences of Symmetry: Irreducible Representations . . . . . . . . . . . . 17
4.5 Complete Set of Commuting Operators . . . . . . . . . . . . . . . . . . . . . . . . . 19

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CHEM400/740: Quantum Mechanics in Chemistry 2021 Winter

1. Review Session

The full electronic Hamiltonian:

𝐻ˆ = ℎ̂ + 𝑉ˆ (1)

• The two­electron operator:

1Õ 1
𝑉ˆ = (2)
2 𝑖≠ 𝑗 𝑟𝑖 𝑗

• The one­electron operator:

Õ
ℎ̂ = ℎ̂(𝑖) (3)
𝑖

NOTE: sum over all electrons.

• The individual one­electron operator includes kinetic energy and potential energy of nuclei and
electrons:
1
ℎ̂(1) = − ∇12 + 𝑣 Ne
(1) (4)
2
Solve the one­electron Schrödinger equation:

ℎ̂(1)𝜓𝑎 (1) = 𝜀 𝑎 𝜓𝑎 (1) (5)

NOTE:
𝑎 = 1, 2, 3, · · · , 𝑀 (finite in ‘finite basis’)
Add spin: 𝜓𝑐 (𝑟 1 )𝛼 → 𝜓𝑐 (1).
𝜓𝑐 (𝑟 1 ) 𝛽 → 𝜓¯𝑐 (1).

Any product function:

Ö
𝜓𝜆 = 𝜓𝑎𝑖 (𝑟𝑖 )𝜎𝑘 (6)
𝑘∈𝜆

NOTE:
𝜆 indicates a configuration of the orbitals that are occupied.
𝜎𝑘 includes spin up, 𝛼, and spin down, 𝛽.
Í
Each of the product, 𝜓𝜆 , is the eigenfunction of Hamiltonian with eigenvalue, 𝑖∈𝜆 𝜀𝑎𝑖 .

Antisymmetry requirement:

|𝜙𝜆 i = 𝐴𝜓
ˆ 𝜆 (7)

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Õ
𝑁!
𝐴ˆ = (−1) 𝑝 𝑘 𝑃ˆ𝑘 (8)
𝑘

NOTE:
𝐴ˆ represents antisymmetrization operator.
𝑝𝑖 is called the parity of the permutation (0 or 1).
𝑁! is the total number of permutation of N electrons.
(+) sign: even number of interchanges
(−) sign: odd number of interchanges.

Or use Slater determinants:

|𝜙𝜆 i = |𝜓𝑎 (1)𝜓 𝑏 (2) · · · 𝜓¯𝑖 · · · 𝜓¯𝑍 (𝑁)| (9)

a) interchange of electron­label.
b) interchange of spin­orbitals.
=⇒ The easiest way to label about spin.

These are building blocks of electronic structure theory!

2. Full Configuration Interaction

2.1 Orders of the orbitals

Rewrite the eigenfunction of Hamiltonian:

𝐻𝜓
ˆ = 𝐸𝜓 (10)

Multiply by the phase factor, a complex number:

ˆ 𝑖𝜓 𝜓 = 𝐸𝑒𝑖𝜓 𝜓
𝐻𝑒 (11)

NOTE:
𝑒𝑖𝜓 𝜓 is also the eigenstate.
𝑒𝑖𝜓 : arbitrary phase.
even scaling factor =⇒ change norm of the wavefunction, 𝜓.

We can order the orbitals, as changing the order in a determinant introduces a sign at most. In­

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cluding spin, we might also say:

|𝜙𝜆 i = |𝜓𝑎 (1)𝜓 𝑏 (2) · · · 𝜓 𝑍 (𝑁𝛼 ) 𝜓¯𝑎 0 (1) 𝜓¯𝑏 0 (2) · · · 𝜓¯𝑍 (𝑁 𝛽 )i (12)

NOTE:
First includes 𝑁𝛼 electrons with 𝛼 orbitals, then 𝑁 𝛽 electrons with 𝛽 orbitals.

• If we have M spatial orbitals, the number of distinct determinants with 𝑁𝛼 , 𝑁 𝛽 is 𝑁𝑀𝛼 , 𝑁𝑀𝛽 .
Í
The number of determinants is gigantic. Each of these determinants is eigenstate of ℎ̂ = 𝑖 ℎ̂(𝑖)
Í
with energy, 𝑖 𝜀𝑖 . Also, eigenstates of ˆ𝑠 𝑍 = 12 (𝑁𝛼 − 𝑁 𝛽 ). One has to use correct orbitals!

• If the orbitals are chosen to be orthonormal, these states are orthogonal. To normalize one has to
introduce a factor √1 . (proof later)
𝑁!
1) Orthonormality of orbitals:
∫
h𝜓𝑎 |𝜓 𝑏 i = 𝜓𝑎∗ (®
𝑟 )𝜓 𝑏 (®
𝑟 )𝑑 3𝑟 = 𝛿𝛼𝛽 (13)

NOTE:
∫
𝜓𝑎∗ (®
𝑟 )𝜓 𝑏 (®
𝑟 )𝑑 3𝑟 is called overlap integral.
2) Non­orthonormality of orbitals:

h𝜓𝑎 | 𝜓¯𝑏 i = h𝜓𝑎 𝛼|𝜓 𝑏 𝛽i = h𝜓𝑎 |𝜓 𝑏 ispatial h𝛼|𝛽i = 0 (14)

|{z}
0

NOTE:
Orbitals with different spin are always orthogonal. =⇒ h𝛼|𝛽i = 0.
3) If orbitals satisfy ℎ̂(1)𝜓𝑎 (1) = 𝜀 𝑎 𝜓𝑎 (1) and 𝜀 𝑎 ≠ 𝜀 𝑏 , we can get the overlap of the eigen­
functions, h𝜓𝑎 |𝜓 𝑏 i = 0, where ℎ̂(1) is the Hermitian operator.
4) If orbitals satisfy ℎ̂(1)𝜓𝑎 (1) = 𝜀 𝑎 𝜓𝑎 (1) and 𝜀 𝑎 = 𝜀 𝑏 , we can always make such orbitals
orthogonal/ orthonormal, h𝜓𝑎 |𝜓 𝑏 i = 𝛿𝑎𝑏 , where ℎ̂(1) is the Hermitian operator.
Proof:

ℎ̂(𝑐 1 𝜓𝑎 + 𝑐 2 𝜓 𝑏 )
= 𝑐1 𝜀 𝑎 𝜓𝑎 + 𝑐2 𝜀 𝑏 𝜓𝑏
= 𝜀 𝑎 (𝑐 1 𝜓𝑎 + 𝑐 2 𝜓 𝑏 ) (15)

Any linear combination of degenerate orbitals is also eigenstate.

=⇒ Use this to create orthonormal set.
(
1 𝑎=𝑏
In general, h𝜓𝑎 |𝜓 𝑏 i = 𝛿𝑎𝑏 =
0 otherwise

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• The determinants, |𝜙𝜆 i = √1 𝐴(𝜓

ˆ 𝑎 (1) · · · 𝜓 𝑍 (𝑁)), use orthonormal basis for Hilbert space. In
𝑁!
many­electron system, creating the orthonormal basis is convenient to consider and calculate,
hence h𝜙𝜆 |𝜙 𝜇 i = 𝛿𝜆𝜇 .

2.2 Two­electron Interaction

Inclusion of electron repulsion in Hamiltonian:

1Õ 1
𝑉ˆ = (16)
2 𝑖≠ 𝑗 𝑟𝑖 𝑗

Application of the linear variation principal: the full configuration interaction(CI) model of quan­
tum chemistry.
The eigenstates of one­electron Hamiltonian can be used as a basis to set expansion functions for
the true many­electron problem. Then, we can make linear combination:
Õ
|𝜓i = 𝑐𝜆 |𝜙𝜆 i (17)
𝜆

NOTE:
The 𝑐𝜆 are coefficients to be determined.
The |𝜙𝜆 i form an in principal complete basis.
To obtain the coefficients we can apply variational principal. We need to get the expectation value
of the Hamiltonian (energy) and minimize the energy.

h𝜓| 𝐻|𝜓i
ˆ
= h𝐻i = 𝐸 (18)
h𝜓|𝜓i

This leads to a matrix eigenvalue problem. More details see Materials: “Modern Quantum Chem­
istry” Chapter#1 (Szabo and Ostlund).
Õ
h𝜙𝜆 | 𝐻|𝜙
ˆ 𝜇 i𝑐 𝜇 = 𝐸𝑐𝜆 (19)
𝜇
𝐻𝐶 = 𝐶𝐸 (20)

• The orthonormal basis has no overlap matrix.

• The Equation (20) is the Heisenberg version of Quantum Mechanics. This is also called “matrix­
mechanics”.
• Compared with the Schrödinger equation, 𝐻𝜓 ˆ = 𝐸𝜓, both equations are equivalent and need to
solve matrix eigenvalue problem. The Schrödinger equation is called “wave­mechanics”.
• In actual research, we never use Schödinger equation. The research always uses matrix­eigenvalue
equations to calculate by computers. This becomes a nice problem in linear algebra.

This presents the best solution within the basis set.

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2.3 Excited Determinants and Full Configuration Intereaction

If we assume we have M orbitals of both 𝛼 spin and 𝛽 spin. This is determined by basis set used
tp expand orbitals.

𝑀 spatial orbitals
𝑁𝛼 𝛼 electrons
𝑁𝛽 𝛽 electrons
(𝑁𝛼 − 𝑁 𝛽 ) = 2h𝑆 𝑍 i (21)

The number of determinants / the number of coefficients:

! !
𝑀 𝑀
·
𝑁𝛼 𝑁𝛽

• Choose 𝑁𝛼 𝛼­orbitals out of 𝑀.

• Choose 𝑁 𝛽 𝛽­orbitals out of 𝑀.

Example for ethylene:

𝑀 ≈ 100
𝑁𝛼 ≈ 10 = 𝑁 𝛽



100 = 100·99···91 ≈ 100 10 = 1010
10 10·9···1 10
The number of determinants = 1010 × 1010 = 1020
The number of matrix­elements = h𝜙𝜆 | 𝐻|𝜙
ˆ 𝜇 i ≈ 1020 · 1020 = 1040

Absolutely impossible to store Hamiltonian matrix, let alone diagonalize. Even to store solution,
𝑐 𝜇 , is impractical / impossible.

This is called full CI solution, such calculations are done for small molecules or small basis sets.

• FCI: In principle, the full CI is exact solution in complete one­particle basis

­ Exact solution in finite / small basis set.=⇒ A rigorous benchmark to compare against.
­ Conceptually simple. Insight in solutions to S.E.
­ Only requires h𝜙𝜆 | 𝐻|𝜙
ˆ 𝜇 i. Rest in linear algebra can be used in computer science.
• CAS­CI: Take small set of ‘active’ orbitals and ‘active’ electrons. Next, do Full CI for subprob­
lem. Combine CAS­CI with other methods, like: DFT, perturbation theory, and coupled cluster.
These methods can be excellent for very hard problems.

It is evident one needs to make approximations. We will see how to do this without loosing accuracy
(much).

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3. Hartree­Fock Approximation

This is a cornerstone of most wave function based on electronic structure approaches. |𝜓 𝐻𝐹 i is

approximated by a single determinant, |𝜙i. Choose the orbitals 𝜓𝑎 , 𝜓 𝑏 , · · · , 𝜓 𝑍 .

1
|𝜙i = √ |𝜓𝑎 (1)𝜓 𝑏 (2) · · · 𝜓 𝑍 (𝑁)| (22)
𝑁!
The orbitals are optimized such that the energy is minimized. Hence, the energy for full Hamil­
tonian, h𝜙| 𝐻|𝜙i
ˆ is minimum. We do not solve for one electron, like ℎ̂𝜓𝑎 = 𝜀 𝑎 𝜓𝑎 , because they do not
take into account the repulsion between electrons and electrons, 𝑉ˆ𝑒𝑒 . Also, orbitals are orthonormal,
h𝜓𝑎 |𝜓 𝑏 i = 𝛿𝑎𝑏 .
I will briefly state the equations of Hartree­Fock approximation, we will discuss in more details
later.
Firstly, expand the molecular orbitals in basis set and introduce a finite atomic basis set, | 𝜒𝜇 i.
We might choose basis set 6­31g(d,p) or cc­pvtz in Gaussian as an input to do some calculations (fixed
by nuclear configurations).
Õ
𝜓𝑎 (1) = 𝜒𝜇 (1)𝑐 𝜇𝑎 (23)
𝜇

Molecular orbitals are linear combinations of atomic orbitals.

Here are some important quantities in AO­basis we can calculate:

• Overlap integral:

h𝜒𝜇 | 𝜒𝑣 i = 𝑆 𝜇𝑣 (24)

• One­electron integrals:
∫
h𝜒𝜇 | ℎ̂| 𝜒𝑣 i = ℎ̂ 𝜇𝑣 = 𝜒𝜇∗ (1) ℎ̂(1) 𝜒𝑣 (1)𝑑1 (25)

• Two­electron integrals:
∫
1 1
h𝜒𝜇 𝜒𝑣 | | 𝜒𝜆 𝜒𝜎 i ≡ h𝜇𝑣|𝜆𝜎i = 𝜒𝜇∗ (1) 𝜒𝑣∗ (2) 𝜒𝜆 (1) 𝜒𝜎 (2)𝑑1𝑑2 (26)
𝑟 12 𝑟 12

NOTE:
𝜒𝜇 indicates spin­orbital here.
We can also use round brackets to describe two­electron integral, (𝜇𝜆|𝑣𝜎). They are same
integral.

(𝜇𝜆|𝑣𝜎) = h𝜇𝑣|𝜆𝜎i (27)

| {z } | {z }
(11|22) h12|21i

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• Anti­symmetrized two­electron integrals:

h𝜇𝑣||𝜆𝜎i = h𝜇𝑣|𝜆𝜎i − h𝜇𝑣|𝜎𝜆i (28)

These AO­integrals are calculated at the start of a calculation.

A Hartree­Fock calculation follows Self­consistent procedure.

3.1 Self­consistent Procedure

Assume a guess for molecular orbitals, the molecular coefficient, 𝐶 𝜇𝑖 (𝑖 = 1, 𝑁 and 𝜇 = 1, 𝑁).

1) Calculate density matrix for occupied orbitals:

Õ
𝐷 𝜇𝑣 = 𝐶 𝜇𝑖 𝐶𝑣𝑖 (29)
𝑖=1,𝑁

2) Calculate Fock­matrix:
Õ
𝐹𝜇𝑣 = ℎ̂ 𝜇𝑣 + h𝜇𝜆||𝑣𝜎i𝐷 𝜆𝜎 (30)
𝜆𝜎

3) Solve (generalized) eigenvalue problem:

Õ Õ
𝐹𝜇𝑣 𝐶𝑣𝑖 = 𝑆 𝜇𝜆 𝐶𝜆𝑖 𝜀𝑖 (31)
𝑣 𝜆

=⇒ Molecular orbitals 𝐶𝑣𝑖 , Orbital energies 𝜀𝑖

If new orbitals (𝐶𝑣𝑖 ) from step 3) agree with input orbitals (𝐶 𝜇𝑖 ), they are converged. The con­
verged result is the correct HF solution.
Otherwise go back to step 1). Iterate until 𝐹, 𝐷, 𝐶 no longer change.
This is called a self­consistent filled procedure.
At self consistency, 𝐷 (in) −→ 𝐹 −→ Diagonalize −→ 𝐷 (out) . When 𝐷 (in) = 𝐷 (out) , the
energy of determinant is optimal (stationary).

In practice one uses smart converge techniques. HF calculations are cumbersome sometimes.
NOTE (More discussion later):

­ The determinant in HF is unique (up to a phase).

­ The density matrix is unique (given the basis set).
­ Molecular orbitals are not unique.
Õ
∗
𝐶 𝜇𝑖 𝐶𝑣𝑖 = 𝐷 𝜇𝑣 (32)
𝑖

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One can ritate occupied orbitals.

Õ
0
𝐶 𝜇𝑖 = 𝐶 𝜇 𝑗 𝑢 𝑗𝑖 (33)
𝑖

Note that the 𝑢 𝑗𝑖 is unitary.

Hartree­Fock in practice:

­ Decent results for geometry optimization (small basis set).

­ Reasonable harmonic frequencies.
­ Very poor for thermo chemistry, energy differences.
­ Not good for potential energy surface.

However, total energies in HF are remarkably accurate.

𝐸 HF ⪆ 99.5% of 𝐸 FCI (34)

Total energies are huge. For this reason HF by itself is not good enough. One needs to go beyond:
inclusion of electron correlation. Also, HF calculation is often the starting point.

4. Symmetry in Quantum Mechanics

This us a vast topic. I wish to discuss have the general principles. I will not go into full detail. In
a next section, I will discuss the permutation group, angular momentum and spin.

4.1 General Principal of Symmetry

Suppose that we know the solutions to the S.E.

𝐻|𝜙
ˆ 𝑛 i = 𝐸 𝑛 |𝜙𝑛 i (35)
h𝜙𝑛 |𝜙𝑚 i = 𝛿𝑛𝑚 (36)

These solutions form an orthonormal basis for the Hilbert space.

Question:
Can I find operators 𝑢ˆ such that 𝑢ˆ|𝜙𝑛 i also form an orthonormal basis, while having the same
energies 𝐸 𝑛 ?

(|𝜙𝑚 i) † = h𝜙𝑚 | 𝑢ˆ† 𝑢ˆ = 1 (37)

( 𝑢ˆ|𝜙𝑚 i) † 𝑢ˆ|𝜙𝑛 i = h𝜙𝑚 | 𝑢ˆ† 𝑢ˆ|𝜙𝑛 i = 𝛿𝑚𝑛 (38)
𝐻ˆ 𝑢ˆ|𝜙𝑛 i = 𝐸 𝑛 𝑢ˆ|𝜙𝑛 (39)

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NOTE:

1) The orthonormal condition implies:

h𝜙𝑚 | 𝑢ˆ† 𝑢ˆ|𝜙𝑛 i = h𝜙𝑚 |𝜙𝑛 i (40)

𝑢ˆ is a unitary operator: 𝑢ˆ† 𝑢ˆ = 1 and 𝑢ˆ† = 𝑢ˆ−1 . Note that the unitary operators preserve orthonor­
mality of a basis, which means 𝑢ˆ† ≠ 𝑢ˆ in general and 𝑢ˆ−1 ≠ 𝑢ˆ in general.
Reflection in a plane is its own inverse.
Unitary in linear algebra preserves angles and length of a set of vector when general rotation.
In physics some symmetries are anti­unitary (time­reversal) then h𝑢𝜙|𝑢𝜓i = h𝜙|𝜓i ∗ This is not
our usual inner product.
2) 𝑢ˆ commutes with 𝐻. ˆ

𝐻ˆ ( 𝑢ˆ|𝜙𝑛 i) = ( 𝑢ˆ|𝜙𝑛 i)𝐸 𝑛

= 𝑢ˆ𝐻|𝜙
ˆ 𝑛i ∀𝜙𝑛 (41)
𝐻ˆ 𝑢ˆ = 𝑢ˆ𝐻ˆ (42)
 
𝐻,
ˆ 𝑢ˆ = 0 (43)

This is true for all |𝜙𝑛 i.

3) If 𝑢ˆ commutes with 𝐻, ˆ then also 𝑢ˆ† = 𝑢ˆ−1 .

𝐻ˆ 𝑢ˆ = 𝑢ˆ𝐻ˆ (44)
𝑢ˆ−1 𝐻ˆ 𝑢ˆ = 𝑢ˆ−1 𝑢ˆ𝐻ˆ = 𝐻ˆ (45)

𝑢ˆ−1 𝐻ˆ ( 𝑢ˆ𝑢ˆ−1 ) = 𝐻ˆ 𝑢ˆ−1 (46)

𝑢ˆ−1 𝐻ˆ = 𝐻ˆ 𝑢ˆ−1 (47)
𝑢ˆ† 𝐻ˆ = 𝐻ˆ 𝑢ˆ† (48)

4) If 𝑢ˆ1 and 𝑢ˆ2 commute, and unitary, then also 𝑢ˆ1 𝑢ˆ2 .
a) 𝐻ˆ 𝑢ˆ1 𝑢ˆ2 = 𝑢ˆ1 𝐻ˆ 𝑢ˆ2 = 𝑢ˆ1 𝑢ˆ2 𝐻ˆ
b) ( 𝑢ˆ1 𝑢ˆ2 )( 𝑢ˆ1 𝑢ˆ2 ) † = 𝑢ˆ1 𝑢ˆ2 𝑢ˆ†2 𝑢ˆ†1 = 𝑢ˆ1 𝑢ˆ†1 = 1
NOTE:
𝑢ˆ†1 𝑢ˆ†2 𝑢ˆ1 𝑢ˆ2 ≠ 1
5) Linear operators are associative.

𝑢ˆ1 ( 𝑢ˆ2 𝑢ˆ3 ) = ( 𝑢ˆ1 𝑢ˆ2 ) 𝑢ˆ3 = 𝑢ˆ1 𝑢ˆ2 𝑢ˆ3 (49)

Always holds for matrix multiplication.

It follows that the (full) set of symmetry operations 𝑢ˆ𝑖 form a mathematical group.

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4.2 Group

Definition of a group:
Set elements {𝑔𝑖 } form a group iff:

1) 𝑔𝑖 𝑔 𝑗 ∈ 𝑔 if 𝑔𝑖 and 𝑔 𝑗 is 𝑔.
2) 𝑔𝑖 (𝑔 𝑗 𝑔𝑢 ) = (𝑔𝑖 𝑔 𝑗 )𝑔𝑢 = 𝑔𝑖 𝑔 𝑗 𝑔𝑢 (Associative)
3) ℎ𝑎𝑡𝐼 ∈ 𝑔, 𝑔𝑖 · 𝐼ˆ = 𝐼ˆ · 𝑔𝑖 = 𝑔𝑖
4) 𝑔𝑖−1 ∈ 𝑔, 𝑔𝑖−1 · 𝑔𝑖 = 𝐼ˆ

The theory of groups ⇐⇒ The theory of symmetry

More details about Groups (Mathematical):

See Link: Wikipedia Website Link on Groups (Mathematical)

Example of a group(1):
Elements of 𝑧 {0, ±1, ±2, ±3}.
𝑔𝑖 ⊗ 𝑔 𝑗 , ⊗ means group multiplication.
𝑧𝑖 + 𝑧 𝑗
Whole numbers from a group under addition:
𝑧1 , 𝑧2 𝑧1 + 𝑧2 ∈ 𝑍
𝑧1 + (𝑧2 + 𝑧3 ) Associative
𝐼ˆ = 0 0 + 𝑧1 = 𝑧1
𝑧1 + (−𝑧1 ) = 0 =⇒ 𝐼ˆ

Example of a group(2):
Another group: rational numbers, excluding 0 under multiplication.
𝑥, 𝑦 −→ 𝑧 rational
𝑥(𝑥 −1 ) = 1, with identity, 1. (𝑥 · 1 = 1 · 𝑥 = 1)
Why is 0 excluded? 0−1 =?

4.3 Example of Groups in Physics

Symmetries in physics Conservation Laws (Noether Theorem)

Translational Conservation of Linear Momentum
Rotations Angular Momentum is Conserved
Translation in Time Conservation of Energy
Rotation of Electron Spin Conservation of Spin­angular Momentum

• Overall translation, 𝑥® −→ 𝑇ˆ𝑎 𝑥® = 𝑥® + 𝑎®

(𝑇ˆ𝑎 𝜓)(𝑇ˆ𝑎 𝑥) ≡ 𝜓(𝑥) (50)

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NOTE:
𝑇ˆ𝑎 𝜓: translated function.
Translated function in translated point has value of original function in original point.

𝑇ˆ𝑎−1𝑇ˆ𝑎 𝜓(𝑇ˆ𝑎 𝑥) = 𝑇ˆ𝑎−1 𝜓(𝑥) (51)

𝜓(𝑇𝑎 𝑥) = 𝑇ˆ𝑎−1 𝜓(𝑥) (52)
𝑇ˆ𝑏 = 𝑇ˆ𝑎−1 (53)
𝑇ˆ𝑏 𝜓(𝑥) = 𝜓(𝑇ˆ𝑏−1 𝑥) (54)

This is general definition (Equation 54) of operator on a function, if one knows the operation on
coordinates.
• Overall Rotation (nuclei + electrons)

𝑅𝜓(𝑥) = 𝜓(𝑅 −1 𝑥) (55)

Rotations are associated with angular momentum theory, like 𝐿 ˆ𝑥, 𝐿

ˆ 𝑦, 𝐿
ˆ 𝑧, 𝐿
ˆ 2 . All of angular mo­
mentum theory from commutation relations, [ 𝐿
ˆ𝑥, 𝐿
ˆ 𝑦 ] = 𝑖ℏ 𝐿
ˆ 𝑧.
• Multiplication by a phase

𝜓i = 𝑒𝑖𝜙 |𝜓i (56)

Same phase for every state.

This is origin of gauge theories, electron­magnetism.
• Permutations of electronic coordinates.

𝑃ˆ𝜆 𝜓(𝑥1 , 𝑥 2 , ..., 𝑥 𝑁 ) = 𝜓( 𝑃ˆ𝜆−1 (𝑥1 , ..., 𝑥 𝑁 )) (57)

• Overall rotation of electron spin, for example definition of the z­axis for 𝑠 𝑍 operator.
This is the conservation of spin­angular momentum. ˆ𝑠 𝑧 , ˆ𝑠𝑥 , ˆ𝑠 𝑦 , ˆ𝑠2 commute with the 𝐻.
ˆ We can
use them to build a “rotation group” in spin space. Analogy to rotation in space, you need to
rotate around 4𝜋 to get the identity.
• Point group symmetry in Chemistry. If one rotates nuclei and electrons, Hamiltonian is invariant.
Now rotate only electronic part of the wave function. Equivalently rotate nuclei in opposite
position.

𝑅𝜓(®
ˆ 𝑟 , 𝑄 𝛼 ) = 𝜓(®
𝑟 , 𝑅𝑄 𝛼 ) (58)

Hamiltonian is invariant under operations. It means nuclei map onto one another.
Point group of molecule:

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(a) Water, 𝐶2𝑣 (b) Benzene, 𝐷 6ℎ

Figure 1 Point Group of Molecules

More details about Groups in Physics:

See Link: Wikipedia Website Link on Groups in Physics

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4.4 Consequences of Symmetry

Summary 4.1

Summary of Symmetry Considerations (Abstract Discussion)

1) Unitary operators preserve orthonormality of a basis.

𝑢ˆ† 𝑢ˆ = 𝐼; 𝑢ˆ† = 𝑢ˆ−1

h𝜙 𝑘 | 𝑢ˆ† 𝑢ˆ|𝜙𝑙 i = h𝜙 𝑘 |𝜙𝑙 i = 𝛿 𝑘𝑙

if original basis is orthonormal.

 
2) If 𝐻,ˆ 𝑢ˆ = 0, then if 𝐻|𝜓i
ˆ = 𝐸 |𝜓i.

𝐻ˆ ( 𝑢ˆ|𝜓i) = 𝐸 ( 𝑢ˆ|𝜓i)

𝑢ˆ|𝜓i is eigenstate of 𝐻ˆ with the same energy 𝐸.

 
3) If unitary 𝑢ˆ1 , 𝑢ˆ2 and 𝐻,
ˆ 𝑢ˆ𝑖 = 0, 𝑖 = 1, 2. Then,

𝑢ˆ3 = 𝑢ˆ1 𝑢ˆ2

a) 𝑢ˆ3 is a unitary.
b) 𝑢ˆ3 commutes with 𝐻. ˆ
4) 𝑢ˆ† = 𝑢ˆ−1 is unitary and commutes with 𝐻.
ˆ
5) 𝐼 is unitary and commutes with 𝐻.ˆ

⇒ The set of symmetry operators 𝑢ˆ𝑖 form a mathematical group.(Statement 2­5: postulates that
define a mathematical group.)
⇒ All aspects of group theory (a part of algebra) apply to symmetry in Quantum Mechanics.

What if 𝐸 𝑛 is non­degenerate?

4.4.1 Example: Particle on a Ring

The Schrödinger equation of a particle on a ring:

ℏ2 𝑑 2 𝜓(𝜙)
− = 𝐸𝜓(𝜙) (59)
2𝑚𝑅 2 𝑑 (𝜙) 2
ℏ2 𝑑 2 𝐿
ˆ𝑧
𝐻ˆ = − = (60)
2𝑚𝑅 2 𝑑𝜓 2 2𝑚𝑅 2
ˆ 𝑧 = −𝑖ℏ 𝜕
𝐿 (61)
𝜕𝜓
𝐼 = 𝑚𝑅 2
(62)

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Figure 2 The energy level of a particle on a ring.

The eigenfunctions corresponding to +𝑚 and 𝑚 are linearly independent, so both must be accepted.
Therefore all eigenvalues, except 𝐸 0 , are two­fold (or doubly) degenerate. The eigenfunctions can all
be written in the form const 𝑒𝑖𝑘 𝜙 , with 𝑚 allowed to take either positive and negative values (or 0).
NOTE:
The degeneracy of 2 means that two different wave functions with same eigenvalues.
Different wave functions mean more different than overall phase.
NOT different: |𝜙𝑛 i −→ (𝑒𝑖𝑘 𝜙 )|𝜙𝑛 i is also eigenstate.
Degenerate states: choose the orthonormal.

General solution:

𝑓 (𝜙) = 𝑐 1 𝑒𝑖𝑘 𝜙 + 𝑐 2 𝑒 −𝑖𝑘 𝜙 (63)

Solutions are not unique. Consider:

( (
𝑠𝑖𝑛(𝑘 𝜙) 𝑒𝑖𝑘 𝜙
or
𝑐𝑜𝑠(𝑘 𝜙) 𝑒 −𝑖𝑘 𝜙

1 𝑖𝑘 𝜙
𝑐𝑜𝑠(𝑘 𝜙) = (𝑒 + 𝑒 −𝑖𝑘 𝜙 ) (64)
2
1
𝑠𝑖𝑛(𝑘 𝜙) = (𝑒𝑖𝑘 𝜙 − 𝑒 −𝑖𝑘 𝜙 ) (65)
2

The set of solutions / the subspace of solutions that we choose is unique.

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Summary 4.2

The solution of a particle on a ring:

√1 𝑒𝑖𝑘 𝜙 and √1 𝑒 −𝑖𝑘 𝜙 are eigenstates of 𝐻 𝑘 2 ℏ2 𝑘 2 ℏ2
ˆ with the same eigenvalue (energy), (
2𝑚𝑅 2 2𝐼
).
2𝜋 2𝜋
Freedom in choice according to different basis sets or different subspaces:
a) Real eigenfunctions:

 1
 √ 𝑠𝑖𝑛(𝑘 𝜙)


 𝜋 1
𝑘=0: √

 1 2𝜋
 √𝜋 𝑐𝑜𝑠(𝑘 𝜙)


b) Eigenstates of 𝐿
ˆ 𝑧:

 1 𝑖𝑘 𝜙

 √ 𝑒

 2𝜋

 1 −𝑖𝑘 𝜙
√ 𝑒

 2𝜋
c) Other choice, for example :

 1

 √ 𝑠𝑖𝑛(𝑘 𝜙 + 𝛼)

 𝜋

 1
 √𝜋 𝑐𝑜𝑠(𝑘 𝜙 + 𝛼)


𝛼 for arbitrary.

More details about Particle on a Ring, see Link: Particle on a Ring.

4.4.2 Consequences of Symmetry: Multiplet

Consider a multiplet of eigenstates of Hamiltonian, |𝜙 𝑘 i, all with same energy, 𝐸. The number of
orthonormal states is well defined as degeneracy. States themselves are called freedom. The space it
spans is always the same.
Õ
|𝜙 𝑘 ih𝜙 𝑘 = 𝑃ˆ𝐸 (66)
𝑘 ∈𝐸

NOTE:
𝑃ˆ𝐸 is a projector on this space.
Then for any symmetry operator 𝑢ˆ𝑎 :

𝐻ˆ ( 𝑢ˆ𝑎 |𝜙𝑛 i) = 𝐸 𝑛 |( 𝑢ˆ𝑎 |𝜙𝑛 i) (67)

Hence, 𝑢ˆ𝑎 is a linear combination of states in the multiplet.

Õ
𝑢ˆ𝑎 |𝜙𝑙 i = |𝜙𝑙 ih𝜙𝑙 | 𝑢ˆ𝑎 |𝜙 𝑘 i
𝑙∈𝑃 𝐸

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Õ
𝑎
= |𝜙𝑙 i 𝑢ˆ𝑙𝑚 (68)
𝑙∈𝑃 𝐸

Likewise:
Õ
𝑢ˆ𝑏 |𝜙𝑙 i = 𝑏
|𝜙𝑚 i 𝑢ˆ𝑚𝑙 (69)
𝑙∈𝑃 𝐸

The important point is that 𝑢ˆ|𝜙 𝑘 i cab always be expressed in terms of the states in the multiplet.
−→ Stay in the subspace.
Õ
𝑢ˆ𝑏 𝑢ˆ𝑎 |𝜙𝑙 i = |𝜙𝑚 ih𝜙𝑚 | 𝑢ˆ𝑏 |𝜙𝑙 ih𝜙𝑙 | 𝑢ˆ𝑎 |𝜙 𝑘 i (70)
𝑚,𝑙∈𝑃 𝐸
Õ
𝑏 𝑎
= |𝜙𝑚 i 𝑢ˆ𝑚𝑙 𝑢ˆ𝑙 𝑘 (71)
𝑚,𝑙∈𝑃 𝐸
𝑏𝑎
≡ |𝜙𝑚 i 𝑢ˆ𝑚𝑘 (72)

It follows that the matrix­elements of the symmetry operator, follow the same multiplication law
as the group.

𝑢ˆ𝑏𝑎 = 𝑢ˆ𝑏 𝑢ˆ𝑎 ∀𝑎, 𝑏 (73)

⇒ Group multiplication ⇐⇒ Matrix multiplication

The dimension of the matrices is the same as degeneracy of Hamiltonian.

4.4.3 Consequences of Symmetry: Irreducible Representations

Group theory: The matrices 𝑢ˆ𝑎 form a representation of a group.

■ Example:
H­atom : 1s (non­degenerate)
Rotations: 1­dimensional matrices (just numbers)
p­orbitals (𝑝 𝑥 , 𝑝 𝑦 , 𝑝 𝑧 ) : 3­dimensional matrices (3­dimensional representation).
d­orbitals (𝑑𝑥𝑦 , 𝑑 𝑦𝑧 , 𝑑𝑥𝑧 , 𝑑𝑥 2 −𝑦2 , 𝑑 𝑧2 ) : 5­dimensional matrices (5­dimensional representation).
⇒ We get the representations of groups.
⇒ Heart of group theory.

If one cannot reduce the set of functions further, i.e one cannot find a new basis in which all ma­
trices 𝑢ˆ𝑎 have a block form. Then the representation is called irreducible.
Functions |𝜙𝑙 i: transform according to irreducible representations.
The eigenstates of the Hamiltonian can always be chosen to transform as irreducible representa­
tions of the symmetry group of 𝐻. ˆ

𝜙𝑛 |𝑛, Γ, 𝑖i (74)

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NOTE:
Γ: irreducible representation.
𝑖: column of irrep.
𝑛: labels different multiplets, different energy 𝐸 𝑛 .

𝑦 𝑙𝑚 (𝜃, 𝜓) Spherical Harmonics (75)

NOTE:
𝑙: label of irrep.
𝑚: different columns of irrep.
For many electron atoms, we use the same angular momentum label 𝑆, 𝑃, 𝐷, 𝐹 and can label
functions as (𝐿, 𝑀).
⇒ irreducible representations (same as orbitals)
For molecules: Orbitals and many­electron wave functions transform as irreducible representa­
tions: 𝐴1 , 𝐵1 , 𝐵2 , 𝐴2 for water, 𝐶2𝑣 etc.
The irreducible representations are determined by the symmetry group. Independent of Hamil­
tonian. One can show:

h𝜙 𝑘 , Γ1 , 𝑖 1 | 𝐻|𝜙
ˆ 𝑙 , Γ2 , 𝑖 2 i = 0 (76)

NOTE:
unless Γ1 = Γ2 same irrep.
unless Γ1 = Γ2 same column.
𝑘 labels different functions all transforming as Γ1 , 𝑖
Only functions that ‘interact’ have the same symmetry. Interaction means make matrix­elements
of Hamiltonian.
⇒ The Hamiltonian is block diagonal in a symmetry­adapted basis.

Example (water, 𝐶2𝑣 ):

Figure 3 Character table for point group C2v.

Only need to diagonalize blocks: cost of diagonalizations ∼ 𝑛3

ℎ blocks: h diagonalizations of ∼ 𝑛/ℎ blocks. cost, ℎ(𝑛/ℎ) 3 = 1 3
ℎ2
𝑛 .

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Symmetry:

a) Symmetry can be very important to use to make calculation more efficient.

b) States can be labelled according to symmetry ⇒ qualitative understanding, degeneracy pattern.

The use of irreducible representations is the most elaborate use of symmetry in Quantum chem­
istry.
⇒ It is all ‘just’ group theory (math). Any correct results in math will never change.

More details about Irreducible Representations:

See Link: Wikipedia Website Link on Irreducible Representations

4.5 Complete Set of Commuting Operators

Alternate way to think of symmetry: complete set of commuting operators.

Let 𝐴,
ˆ 𝐵ˆ be Hermitian operators that commute with 𝐻,
ˆ and also with each other. (unitary operators
are usually not Hermitian)

[ 𝐻,
ˆ 𝐴]
ˆ = [ 𝐻,
ˆ 𝐵]
ˆ = [ 𝐴,
ˆ 𝐵]
ˆ =0 (77)

Example: 𝐻,
ˆ 𝐿ˆ 2, 𝐿
ˆ𝑧

Hermitian operator: 𝑂|𝑂

ˆ 𝑖 i = 𝑂 𝑖 |𝑂 𝑖 i Get eigenvalues and eigenvectors.
Then, we can define a complete set of common eigenstates |𝐸 𝑛 , 𝑎𝑖 , 𝑏 𝑗 i.

𝐻|𝐸
ˆ 𝑛 , 𝑎𝑖 , 𝑏 𝑗 i = 𝐸 𝑛 |𝐸 𝑛 , 𝑎𝑖 , 𝑏 𝑗 i (78)
𝐴|𝐸
ˆ 𝑛 , 𝑎𝑖 , 𝑏 𝑗 i = 𝑎𝑖 |𝐸 𝑛 , 𝑎𝑖 , 𝑏 𝑗 i (79)
𝐵|𝐸
ˆ 𝑛 , 𝑎𝑖 , 𝑏 𝑗 i = 𝑏 𝑗 |𝐸 𝑛 , 𝑎𝑖 , 𝑏 𝑗 i (80)

Simultaneous, eigenstates of 𝐻,
ˆ 𝐴, ˆ 𝐵.
ˆ
h i
If 𝐴,
ˆ 𝐵ˆ have complete set of common eigenstates then 𝐴,
ˆ 𝐵ˆ = 0
h i (1)
𝐴,
ˆ 𝐵ˆ = 0 ⇐=⇒ complete set of common eigenstates
(2)
Proof (1):
Í
Complete basis: |𝜓 = 𝑖, 𝑗 |𝑎𝑖 , 𝑏 𝑗 i𝑐𝑖 𝑗
Any 𝜓 can be expanded in |𝑎𝑖 , 𝑏 𝑗 i

𝐴ˆ 𝐵|𝑎
ˆ 𝑖 , 𝑏 𝑗 i = 𝐴(𝑏
ˆ 𝑗 |𝑎𝑖 , 𝑏 𝑗 i)
= 𝑎𝑖 𝑏 𝑗 |𝑎𝑖 , 𝑏 𝑗 i (81)
𝐵ˆ 𝐴|𝑎
ˆ 𝑖 , 𝑏 𝑗 i = 𝐵(𝑎
ˆ 𝑖 |𝑎𝑖 , 𝑏 𝑗 i)
= 𝑏 𝑗 𝑎𝑖 |𝑎𝑖 , 𝑏 𝑗 i (82)
Õ
( 𝐴ˆ 𝐵ˆ − 𝐵ˆ 𝐴)|𝜓i
ˆ = ( 𝐴ˆ 𝐵ˆ − 𝐵ˆ 𝐴)
ˆ |𝑎𝑖 , 𝑏 𝑗 i𝑐𝑖 𝑗
𝑖, 𝑗

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Õ
= (𝑎𝑖 𝑏 𝑗 − 𝑏 𝑗 𝑎𝑖 i)𝑐𝑖 𝑗 = 0 ∀𝜓 (83)
𝑖, 𝑗

Reverse the order of the eigenvalues, and eigenvalues are numbers.

Proof (2): h i
The converse part: if 𝐴, ˆ 𝐵ˆ = 0, they have a complete set of common eigenstates is most
involved, but instructive:
First, diagonalize the operator 𝐵: ˆ 𝐵|𝑏
ˆ 𝑗 i = 𝑏 𝑗 |𝑏 𝑗 i.
Reverse order: ( 𝐵ˆ† |𝑏𝑖 i) † = h𝑏𝑖 | 𝐵.
ˆ
Hermitian operator: 𝐵ˆ† = 𝐵.
ˆ
Eigenvalues of Hermitian operator are real: 𝐵ˆ† = h𝑏𝑖 |𝑏𝑖 i) † = h𝑏𝑖 |𝑏𝑖∗ = h𝑏𝑖 |𝑏𝑖
Acting with 𝐵ˆ on bra directly.
Analogue: right and left eigenvectors for matrices.
For Hermitian/Symmetric matrices eigenvectors are same (or hermitian conjugate).
Eigenvalues are the same.

h𝑏𝑖 |[ 𝐴,
ˆ 𝐵]|𝑏
ˆ 𝑗i = 0 (84)
h𝑏𝑖 | 𝐴ˆ 𝐵ˆ − 𝐵ˆ 𝐴|𝑏
ˆ 𝑗i = 0 (85)
(𝑏𝑖 − 𝑏 𝑗 )h𝑏𝑖 | 𝐴|𝑏
ˆ 𝑗i = 0 (86)

=⇒ If 𝑏𝑖 ≠ 𝑏 𝑗 , then:

h𝑏𝑖 | 𝐴|𝑏
ˆ 𝑗i = 0 (87)

=⇒ 𝐴ˆ is block diagonal in 𝐵ˆ basis.

Second, diagonalize the 𝐴:
ˆ

𝐴ˆ 𝑏1 𝑏2 𝑏3
𝑏1 x 0 0
𝑏2 0 x 0
𝑏3 0 0 x

𝐴ˆ is block­diagonal.
I can diagonalize each block by itself. This does not change eigenvalue of 𝐵.
ˆ
All states in a 𝑏𝑖 block have same eigenvalues.

𝐴|𝑎
ˆ 𝑖 , 𝑏 𝑗 i = 𝑎𝑖 |𝑎𝑖 , 𝑏 𝑗 i (88)
𝐵|𝑎
ˆ 𝑖 , 𝑏 𝑗 i = 𝑏 𝑗 |𝑎𝑖 , 𝑏 𝑗 i (89)

This procedure can be repeated including additional commuting operators.

Õ Õ
𝐵ˆ |𝑏 𝑗 , 𝑘i𝑐 𝑘 = 𝑏 𝑗 |𝑏 𝑗 , 𝑘i𝑐 𝑘 i
𝑘 𝑘 Õ
= 𝑏𝑗( |𝑏 𝑗 , 𝑘i𝑐 𝑘 ) (90)
𝑘

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i h𝑏 𝑗 is ieigenstate of 𝐵 with eigenvalue 𝑏 𝑗 .

Linear combination of states withh same ˆ
i eigenvalue
h
If three operators are commuting 𝐴, ˆ 𝐵ˆ = 𝐴, ˆ 𝐶ˆ = 𝐵,
ˆ 𝐶ˆ = 0, the complete set of eigenstates
is |𝑎𝑖 , 𝑏 𝑗 , 𝑐 𝑘 i.
=⇒ These all present good quantum numbers.
=⇒ Labels for the states.
e.g. 𝐻, ˆ 𝐿 ˆ 2, 𝐿
ˆ 𝑧 −→ |𝐸 𝑛 , 𝑙, 𝑚i
e.g. 𝑆ˆ12 , 𝑆ˆ𝑧 −→ |𝐸 𝑛 , 𝐿, 𝑀, 𝑆, 𝑀𝑠 i

In a time­dependent formulation h 𝐴i
ˆ and h 𝐵i
ˆ would not depend on time.

ˆ −𝑖 𝐻𝑡 |𝜓(𝑡 = 0)i
= h𝜓(𝑡 = 0)|𝑒𝑖 𝐻𝑡 𝐴𝑒
ˆ ˆ
h𝜓(𝑡)| 𝐴|𝜓(𝑡)i
ˆ
= h𝜓(𝑡 = 0)| 𝐴|𝜓(𝑡
ˆ = 0)i (91)

𝐻ˆ is independent of time.

[ 𝐻,
ˆ 𝐴] ˆ =0 (92)
𝑑h 𝐴i ˆ
=0 (93)
h 𝑑𝑡 i
𝐻, 𝑓 ( 𝐴)
ˆ ˆ =0 𝑓 ( 𝐴):
ˆ Taylor series expansion (94)
h i
𝐻ˆ 𝑛 , 𝐴ˆ =0 (95)

Such operators represent conserved

h quantities.
i
Any Hermitian operator that has 𝐻, 𝐴 = 0 is a conserved quantity.
ˆ ˆ

𝐴ˆ† = 𝐴ˆ (96)
𝑖 𝐴ˆ † ˆ†
(𝑖 𝐴) −𝑖 𝐴ˆ† −𝑖 𝐴ˆ
(𝑒 ) = 𝑒 =𝑒 =𝑒 (97)
𝑖 𝐴ˆ 𝑖 𝐴ˆ † 𝑖 𝐴ˆ −𝑖 𝐴ˆ
𝑒 (𝑒 ) = 𝑒 𝑒 =1 (98)

NOTE:
𝐴:
ˆ hermitian operator.
𝑒𝑖 𝐴 is a symmetry operator, or even 𝑒𝑖 𝐴𝛼 is symmetry operator with real parameter 𝛼.
ˆ ˆ

This is a way to make the connection between symmetries and conserved quantities.

Example(1):
𝐿
ˆ𝑥, 𝐿
ˆ 𝑦, 𝐿
ˆ 𝑧 are hermitian, commute with 𝐻.
ˆ

𝐿
ˆ± = 𝐿 ˆ𝑥 + 𝑖𝐿ˆ𝑦 (99)
𝐿
ˆ + |𝑙, 𝑚i −→ 𝑐 + |𝑙, 𝑚 + 1i 𝐿
ˆ − |𝑙, 𝑚i −→ 𝑐 − |𝑙, 𝑚 − 1i
 
𝐻,
ˆ 𝐿ˆ+ = 0 (100)
 
𝐻,
ˆ 𝐿ˆ− = 0 (101)

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𝐿
ˆ +, 𝐿 ˆ − create new eigenstates with same eigenvalue.
𝑒 𝛼 𝐿 𝑥 +𝛽 𝐿 𝑦 +𝛾 𝐿 𝑧 is an operator that defines wave functions in a rotated frame.
ˆ ˆ ˆ

These symmetries are continuous symmetries group described by linear algebras.

Example(2): h i
1 𝑑2
𝑝 𝑥 commutes with free­particle motion ℎ̂ = − 2 𝑑𝑥 2 , which means 𝑝 𝑥 , ℎ̂ = 0.
ˆ ˆ
𝑒𝑖𝑎ℎ𝑎𝑡 𝑝 𝑥 |𝜓(𝑥)i creates translated function.
𝜕 𝜕 𝜕
𝑒𝑖𝑎 𝑝ˆ𝑥 = 𝑒𝑖𝑎h−𝑖ℏ 𝜕𝑥 | = 𝑒 𝑎ℏ 𝜕𝑥 −→ 𝑒 𝑏 𝜕𝑥 with 𝑏 = 𝑎ℏ (102)

𝜕 𝜕 𝑓 1 2 𝜕2 𝑓 1 𝑛 𝜕𝑛 𝑓
𝑒 𝑏 𝜕𝑥 𝑓 (𝑥) = 𝑓 (𝑥) + 𝑏 + 𝑏 + · · · + 𝑏
𝜕𝑥 2 𝜕𝑥 2 𝑛! 𝜕𝑥 𝑛
= 𝑓 (𝑥 + 𝑏) (103)

NOTE: Taylor series expansion.

There are many aspects to symmetry. We often perceive symmetry as beautiful. The theory of
symmetries is also very beautiful (group theory). For we personally, the study of group theory (inde­
pendent reading class) was the first made me want to be a ‘theoretical chemist’.

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