Exchange Interaction: Orbital Spin
Exchange Interaction: Orbital Spin
Exchange Interaction: Orbital Spin
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
-1-
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 = ⋅
K K ϕ a ( r1 ) ϕb ( r1 ) ϕb ( r2 ) ϕa ( r2 )
* *
J ab = e ∫ dr1 ∫ dr2
2
K K “exchange integral”
r1 − r2
⎛ Ψ1 Ψ 1 Ψ1 Ψ 4 ⎞
⎜ ⎟
⎜ ⎟
⎜ Ψ Ψ Ψ 4 Ψ 4 ⎟⎠
⎝ 4 1
-2-
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
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
-3-
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
More general
By keeping the orbital components
K K fixed.
Orbitals i, j exch = ∑ J ij Si S j exchange Hamiltonian
i, j
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.
-4-