CHEM400/740: Quantum Mechanics in Chemistry

Chapter#03

Marcel Nooijen

Contents
1 Symmetric and Anti­symmetric Representations 2
1.1 Transpositions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2 Projector . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.3 Symmetric and Anti­symmetric Representations . . . . . . . . . . . . . . . . . . . . . 4

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1. Symmetric and Anti­symmetric Representations

1.1 Transpositions

The use of transpositions allows us to characterize the fully symmetric and fully anti­symmetric
representation.
Transposition: 𝑇𝑖 𝑗 .
Interchange coordinates of two particles 𝑖 and 𝑗:

𝑇ˆ𝑖 𝑗 𝜓(1, 2, . . . , 𝑖, . . . , 𝑗, . . . , 𝑁) = 𝜓(1, 2, . . . , 𝑗, . . . , 𝑖, . . . , 𝑁) (1)

Any permutation is a product of transpositions. The number of transpositions is either even or odd.
Parity of permutation with 𝑃𝑖 = 0, 1: 𝑃ˆ𝑖 −→ (−) 𝑃𝑖
Two types of functions represent the permutation group.

1) Symmetric transposition:

𝑇ˆ𝑎 |𝜓 (𝑆) i = |𝜓 (𝑆) 𝑇𝑎 (1, 2, . . . , 𝑁)i

= +|𝜓 (𝑆) i (2)

The symmetric functions are he same under interchange of two coordinates.

2) Anti­symmetric transposition:

𝑇ˆ𝑎 |𝜓 ( 𝐴) i = |𝜓 ( 𝐴) 𝑇𝑎 (1, 2, . . . , 𝑁)i

= −|𝜓 ( 𝐴) i (3)

Antisymmetric functions change sign under interchange of two coordinates.

eg, 𝜓(3, 2, 1) = −𝜓(1, 2, 3)
Since any permutation is a product of transpositions.

𝑃ˆ𝑘 |𝜓 (𝑆) i = +|𝜓 (𝑆) i (4)

𝑃ˆ𝑘 |𝜓 ( 𝐴) i = (−) # of Transp |𝜓 ( 𝐴) i
= (−) 𝑃 𝑘 |𝜓 ( 𝐴) i (5)

One can argue that one can expect this behaviour, by examining eigenfunctions of 𝑇.
ˆ
Eigenfunctions of 𝑇:
ˆ

𝑇ˆ = 𝑇ˆ−1 = 𝑇ˆ† (6)

𝑇ˆ |𝜓i = 𝜆|𝜓i (7)
𝑇ˆ𝑇ˆ |𝜓i = 𝜆2 |𝜓i = |𝜓i (𝑇ˆ2 = 1) (8)
=⇒ 𝜆 = 1 or 𝜆 = −1

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NOTE:
𝑇ˆ is Hermitian and its own inverse.

Since 𝑇ˆ𝑎 commutes with 𝐻, ˆ 𝑇ˆ𝑎 |𝜓i can be chosen either to change sign or stay the same. In practice,
I can make a set of commuting, 𝑇ˆ12 , 𝑇ˆ34 , 𝑇ˆ56 , and demand that 𝜓 is eigenstate of 𝐻ˆ and selected 𝑇. ˆ Then,
one could choose some 𝑇ˆ𝑎 to have some 𝜆 𝑎 = +1 and some 𝑇ˆ𝑎 to have 𝜆 𝑎 = −1. Such eigenfunctions
do exist. However, for |𝜓 (𝑆) , we can get 𝑇ˆ𝑎 |𝜓 (𝑆) i = +|𝜓 (𝑆) i for all 𝑇ˆ𝑎 . For |𝜓 ( 𝐴) , we can get 𝑇ˆ𝑎 |𝜓 ( 𝐴) i =
−|𝜓 ( 𝐴) i. These are the only 1­dimensional irreps of the permutation group.

Lowest degree of representation (degeneracy of 𝐻):

ˆ
1 for Symmetry(S) or Anti­symmetry(A)
(N­1) for N­particles
eg, if 20 electrons =⇒ 19­fold degeneracy (Not obscured in nature)

1.2 Projector

To describe fully symmetric or anti­symmetric wave functions projectors are useful.

Figure 1 Projector on the x,y,z axis

𝑃ˆ𝑥𝑦 : projector on the xy­plane.

Eigenvectors:
Vector onto z­axis: 𝑃ˆ𝑒ˆ𝑧 · 𝑎 = 0 =⇒ 𝜆 = 0.
Vector in the xy­plane: 𝑃ˆ𝑥𝑦 (𝑎 𝑒®𝑥 + 𝑏 𝑒®𝑦 ) = 𝑎 𝑒®𝑥 + 𝑏 𝑒®𝑦 =⇒ 𝜆 = 1

For an orthogonal projector:

𝑝2 = 𝑝 (9)
†
𝑝 =𝑝 (10)

Eigenfunctions of a projector:

𝑝|𝜓i = 𝜆|𝜓i (11)

𝑝 2 |𝜓i = 𝑝 · 𝑝|𝜓i = 𝜆2 |𝜓i
= 𝑝|𝜓i = 𝜆|𝜓i (12)

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⇒(𝜆2 − 𝜆)|𝜓i = 0 (13)

⇒𝜆 = 1 or 𝜆 = 0

𝑝|𝜓i
ˆ = |𝜓i:
|𝜓i is in the subspace defined by 𝑝.ˆ
𝑝(
ˆ 𝑝|𝜓i)
ˆ is eigenvector of 𝑝ˆ with eigenvalue of 1.
𝑝|𝜓i
ˆ = 0:
|𝜓i is orthogonal to subspace defined by 𝑝. ˆ
∑
𝑝ˆ = 𝜆∈subspace |𝜙𝜆 ih𝜙𝜆 | with h𝜙𝜆 |𝜙 𝜇 i = 𝛿𝜆𝜇 .
|ketihbra| is related to projector. |𝜙𝜆 i is orthonormal basis for subspace.

1.3 Symmetric and Anti­symmetric Representations

Here we define projectors on the symmetry(S) and anti­symmetry(A) subspace.

1 ∑ˆ
𝑁!
𝑆ˆ = 𝑃𝑘 (14)
𝑁! 𝑘=1
1 ∑ 𝑃𝑘 ˆ
𝑁!
𝐴ˆ = (−) 𝑃 𝑘 (15)
𝑁! 𝑘=1

In the exercise you will proof that 𝑆/

ˆ 𝐴ˆ are Hermitian and that they satisfy 𝑆ˆ2 = 𝑆;
ˆ 𝐴ˆ2 = 𝐴.
ˆ 𝑝ˆ2 = 𝑝ˆ
is called idempotent.
Let us proof that 𝐴|𝜓i
ˆ is fully antisymmetric, irrespective of |𝜓i. ⇒ To proof: 𝑇ˆ𝑎 ( 𝐴|𝜓i)
ˆ = − 𝐴|𝜓i
ˆ

1 ∑ 𝑃𝑘 ˆ
𝑁!
𝑇ˆ𝑎 ( 𝐴|𝜓i)
ˆ = 𝑇ˆ𝑎 (−) 𝑃 𝑘 |𝜓i
𝑁! 𝑘=1
1 ∑
𝑁!
= (−) (−) 𝑃 𝑘 +1 (𝑇ˆ𝑎 𝑃ˆ𝑘 )|𝜓i (16)
𝑁! 𝑘=1

NOTE:
(−) (−) 𝑃 𝑘 +1 = (−) 𝑃 𝑘 .

Now 𝑇ˆ𝑎 𝑃ˆ𝑘 = 𝑃ˆ𝑙 with parity (−) 𝑃 𝑘 +1 = (−) 𝑃𝑙 . Moreover, 𝑇ˆ𝑎 𝑃ˆ𝑘 runs over all permutations again.
Hence:

1 ∑ 𝑃𝑙 ˆ
𝑁!
𝑇ˆ𝑎 ( 𝐴|𝜓i)
ˆ = (−) (−) 𝑃𝑙 |𝜓i
𝑁! 𝑙=1
= −𝐴|𝜓i ∀𝑇ˆ𝑎 (17)

NOTE:
∑ ˆ ˆ ∑ ˆ
𝑘 𝑃𝑖 𝑃 𝑘 = 𝑙 𝑃𝑙 ∀𝑘.

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This argument is always true for a fixed 𝑃ˆ𝑖 . Also, this is a crucial argument in all these proofs.

If one applies the antisymmetrized 𝐴ˆ to a product of orbitals, one gets:

∑ 𝑁!
ˆ 𝑎 (1)𝜙 𝑏 (2) · · · 𝜙 𝑧 (𝑁)) = 1
𝐴(𝜙 (−) 𝑃 𝑘 𝑃ˆ𝑘 (𝜙𝑎 (1)𝜙 𝑏 (2) · · · 𝜙 𝑧 (𝑁))
𝑁! 𝑘=1
1
= |𝜙𝑎 𝜙 𝑏 · · · 𝜙 𝑧 | (18)
𝑁!
The antisymmetrizer provides a generalization to the Slater determinant concept as it can be applied
to any function, 𝜓(1, 2, · · · , 𝑁). Not only to a product of orbitals.
In chapter 2 S&O, we use 𝐴ˆ with a different normalization.

∑
𝑁!
𝐴ˆ0 = (−) 𝑃 𝑘 𝑃ˆ𝑘 (19)
𝑘=1

1 ˆ0 1 ˆ0 1 ˆ0
Then, since 𝑁! 𝐴 · 𝑁! 𝐴 = 𝑁! 𝐴 , it follows 𝐴ˆ0 𝐴ˆ0 = 𝑁! 𝐴ˆ0. 𝐴ˆ0 is no longer a projector (but simpler
to use).

Summary 1.1
[ ]
𝐻,
ˆ 𝑃ˆ𝑘 = 0 𝑃ˆ†𝑘 𝑃ˆ𝑘 = 1

𝑃ˆ𝑘 forms a symmetric group, 𝑆 𝑁 , 𝑘 = 1 · · · 𝑁!.

This implies that eigenfunctions of 𝐻ˆ can be chosen to transform as irreducible representa­
[ irrep]would never change as all operators in Q.M, 𝐻, and any
tions of permutation group. This ˆ
permutation have the property, 𝑂, ˆ 𝑃ˆ𝑘 = 0. Hence, the irrep would never change.
The only low­dimensional irreps (for many particles) are the fully symmetric and fully anti­
symmetric representation. They are 1­dimensional irreps and allow non­degenerate eigenstates.
For such states, particles are undistinguishable.

|𝜓(1, 2, · · · , 𝑁)| 2 = |𝜓( 𝑃ˆ𝑙 (1, 2, · · · , 𝑁))| 2

Probabilities are unaffected under permutation.

From the spin­satisfies theorem in Quantum­Field theory: (complicated)
• Half­integer­spin particles are Fermions; Antisymmetric irrep.
• Integer­spin particles are Bosons; Symmetric irrep.
For systems like He, Ru atoms, atomic nuclei (made of protons and neutrons, or quarks). One
speaks of bosons made from composite fermions. In my opinion, these are effective theories: The
true wavefunction in terms of elementary particle is anti­symmetric. We can treat the composite
particle as a strongly correlated system and this gives rise to effective boson symmetry. (No good
first­principle )