Exchange Interaction

Consider two-electron states:

Total wave function ϕ ( rK ) χ ( sK ) must be antisymmetric (Pauli principle)
N N
orbital spin
part part

singlet ( s = 0 ) → ( ↑↓ ) → orbital part is symmetric

triplet ( s = 1) → ( ↑↑ ) → orbital part is antisymmetric

The Coulomb interaction between the electrons lifts the degeneracy of the
states with different total spin.
K K
Assume that the one-electron problem is solved: h0ϕa ( r ) = Eaϕ a ( r )
Then construct the two-electron wave function according to
K K K K
ϕa ( r1 ) α ( s1 ) ϕ a ( r2 ) α ( s2 )
Ψ= K K K K
ϕb ( r1 ) α ( s1 ) ϕb ( r2 ) α ( s2 )

a
1, 2: sites
1 2 a, b: eigenstates of single electron problem
b

K K K K
1 ϕ a ( r1 ) α ( s1 ) ϕa ( r2 ) α ( s2 )
Ψ1 = K K K K
2 ϕb ( r1 ) α ( s1 ) ϕb ( r2 ) α ( s2 )
β β
Ψ2 =
α α
α α
Ψ3 =
β β
β β
Ψ4 =
β β

1 K K K K
Ψ1 = α ( s1 ) α ( s2 ) ⎡⎣ϕa ( r1 ) ϕb ( r2 ) − ϕ a ( r2 ) ϕb ( r1 ) ⎤⎦ spin and orbital part factorize: ↑↑
2
1 K K K K
Ψ4 = β ( s1 ) β ( s2 ) ⎡⎣ϕa ( r1 ) ϕb ( r2 ) − ϕ a ( r2 ) ϕb ( r1 ) ⎤⎦ spin and orbital part factorize: ↓↓
2
1
Ψ2 = ⎡⎣ϕ a ( r1 ) ϕb ( r2 ) β ( s1 ) α ( s2 ) − ϕb ( r1 ) ϕ a ( r2 ) α ( s1 ) β ( s2 ) ⎤⎦
2
1
Ψ3 = ⎡⎣ϕa ( r1 ) ϕb ( r2 ) α ( s1 ) β ( s2 ) − ϕb ( r1 ) ϕ a ( r2 ) β ( s1 ) α ( s2 ) ⎤⎦
2

 has to be diagonalized in the subspace Ψ1 , ..., Ψ 4 .

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 e2
Ψi K K Ψi
( r1 − r2 )
e2 1 K K * K * K * K * K e2
dr dr ϕ ( r ) ϕ ( r ) − ϕ ( r ) ϕ ( r ) ⋅
⎡ ⎤
( r1 − rK2 ) 2 2 ∫ 1 ∫ 2 ⎣ a 1 b 2 a 2 b 1 ⎦ ( rK1 − rK2 )
i = 1: Ψ 1 K Ψ = ⋅

⎡⎣ϕa ( rK1 ) ϕb ( rK2 ) − ϕ a ( rK2 ) ϕb ( rK1 ) ⎤⎦

= Cab − J ab
K 2 K 2
K K ϕa ( r1 ) ϕb ( r2 )
where Cab = e ∫ dr1 ∫ dr2
2
K K “Coulomb integral”
r1 − r2

K K ϕ a ( r1 ) ϕb ( r1 ) ϕb ( r2 ) ϕa ( r2 )
* *
J ab = e ∫ dr1 ∫ dr2
2
K K “exchange integral”
r1 − r2

exchange of electron (1) and electron (2), J ab is a cross-term!

e2
No cross-term in Ψ 2 Ψ = Cab
( r1 − r2 ) 2
e2
however Ψ2 Ψ = − J ab
( r1 − r2 ) 3
e2
Ψ4 Ψ = Cab − J ab
( r1 − r2 ) 4
The result can be summarized as:
⎛ 1 0 0 0 ⎞ ⎛ Cab − J ab 0 0 ⎞
⎜ ⎟ ⎜ 0 Cab − J ab 0 ⎟
⎟
0 1 0 0⎟ ⎜
(ε a + ε b ) ⎜⎜ +
0 0 1 0 ⎟ ⎜ 0 − J ab Cab 0 ⎟
⎜⎜ ⎟⎟ ⎜⎜ ⎟
⎝0 0 0 1⎠ ⎝ 0 0 Cab − J ab ⎟⎠

⎛ Ψ1  Ψ 1 Ψ1  Ψ 4 ⎞
⎜ ⎟
⎜ ⎟
⎜ Ψ Ψ Ψ 4  Ψ 4 ⎟⎠
⎝ 4 1

→ Ψ1 and Ψ 4 are eigenstates of  . They are the S Z = ±1 components of the

triplet ε H = ε a + ε b + Cab − J ab ≡ ε tr .

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There remains a 2x2 problem to be solved – the matrices must be diagonalized.
Cab − λ − J ab
= ( Cab − λ ) − J ab 2 = 0
2

− J ab Cab − λ
Cab 2 + λ 2 − 2λ Cab − J ab 2 = 0

2Cab ± 4Cab 2 − 4Cab 2 + 4 J ab 2

λ1/ 2 =
2
= Cab ± J ab
→ ε 2 = ε a + ε b + Cab + J ab ≡ ε s
ε 3 = ε a + ε b + Cab + J ab ≡ ε tr

3 triplet states ε tr = ε a + ε b + Cab − J ab

→ 4 states:
1 singlet state ε s = ε a + ε b + Cab + J ab

if J ab > 0 → ε s > ε tr → ε tr is the ground state → ferromagnetic

J ab < 0 → ε s < ε tr
→ direct exchange in orthogonal orbitals favours ferromagnetism → J ab > 0 .

Eigenstates are:
Ψ1 = 1,1
1
( Ψ 2 + Ψ 3 ) = 1, 0 states can be labeled by their spin
2 components, S , S Z , S is the total spin.
1
( Ψ 2 − Ψ 3 ) = 0, 0
2
Ψ4 = 1, −1

We want to rewrite the  operator in terms of the spin operator S1 , S 2 of the

individual electron spins. The energy difference between the triplet and singlet
states is 2 J ab .
⎛ ε tr = ε a + ε b + Cab − J ab ⎞
⎜ ⎟
⎝ ε s = ε a + ε b + Cab + J ab ⎠
K K
→ we can write  = −2 J ab S1 ⋅ S2
KK K K 2
2 S1S 2 = ( S1 + S 2 ) − S12 − S 2 2
N N
3/ 4 3/ 4
KK 1 K K 2 ⎧ 1 for triplet
x 2 S1S 2 + = ( S1 + S 2 ) − 1 = ⎨
2 ⎩−1 for singlet
K K 2
( S1 + S2 ) = ⎧⎨
2 for triplet
since
⎩0 for singlet

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 ε s + ε tr ε s − ε tr ⎛ K K
1⎞
x = − ⎜ 2 S1S2 + ⎟
2 2 ⎝ 2⎠
K K
= constant − 2 J ab S1 ⋅ S 2

The exchange energy can be expressed in terms of the spin operators.

Within the 4-element subspace, the electron-electron interaction can be described

as an “exchange Hamiltonian” that contains only the spin operators. K K
This appealing possibility was first noticed by Dirac: ex = − J ab S1 ⋅ S2

More general
By keeping the orbital components
K K fixed.
Orbitals i, j  exch = ∑ J ij Si S j exchange Hamiltonian
i, j

The electron-electron interaction can be expressed by spin operators!

J is called the exchange coupling constant.

Once more: This is not the result of a mysterious spin-spin interaction, but the
manifestation of the Coulomb interaction between electrons that are
indistinguishable Fermions → antisymmetric total wave function.

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