Hˆ ( 0 )ψ n( 0 ) = E n( 0 )ψ n( 0 )
∫ψ ψ dv =δ E ≠ E Sistem nondegenerate
( 0 )* ( 0 ) (0) (0)
n m mn; n m
Misalkan Hamiltonian sistem mendapat tambahan, misalnya Ĝ << Ĥ ( 0)
Hˆ = Hˆ ( 0 ) + γ Gˆ γ=1
Hˆ ψ n = ( Hˆ ( 0 ) + γ Gˆ )ψ n = E nψ n
menghasilkan:
Hˆ ψ n = ( Hˆ ( 0 ) + γ Gˆ )ψ n = E nψ n
⎛ ⎞ ⎛ ⎞ ⎛ ⎞⎛ ⎞
H ( 0) ⎜ψ n( 0) + ∑ γ mφ n( m ) ⎟ + γ Gˆ ⎜ψ n( 0) + ∑ γ mφ n( m ) ⎟ = ⎜ E n( 0) + ∑ γ mε n( m ) ⎟⎜ψ n( 0 ) + ∑ γ mφ n( m ) ⎟
⎝ m =1 ⎠ ⎝ m =1 ⎠ ⎝ m =1 ⎠⎝ m =1 ⎠
(Hˆ − E ) ψ = 0
1. γ ( 0) ( 0)
n
( 0)
n
0
2. (Hˆ − E ) φ = −Gˆ ψ + ε ψ
(0) (0)
n γ (1)
n
(0)
n
(1)
n
(0)
n
1
3. (Hˆ − E ) φ = −Gˆ φ + ε ψ + ε φ
( 0) ( 0)
n
( 2)
n γ (1)
n
( 2)
n
( 0)
n
(1) (1)
n n
2
4. (Hˆ − E ) φ = −Gˆφ +ε ψ +ε φ +ε φ . γ
(0) (0)
n
(3)
n
(2)
n
(3)
n
(0)
n
(2) (1)
n n
(1) (2)
n n
3
Koreksi order-1
∫ {(H ) }
− En(0) ψ n( 0)* φn(1) dv = −Gnn + ε n(1)
( 0)
Misalkan: φn =
(1)
∑c
m( ≠n )
nm ψ m(0) → cnm harus ditentukan
2. ∑ nm
c ˆ
H ( 0)
− (
E ( 0)
n ψ ( 0)
m = − G n)
ˆ ψ (0) + ε (1)ψ (0)
n n
m≠ n
∑c (E
m≠n
nm
( 0)
m )
− En(0) ψ m(0) = −Gˆ ψ n(0) + ε n(1)ψ n(0)
∑c (E
m≠n
nm
( 0)
m )
− En(0) ∫ψ k(0)*ψ m(0) dv = −∫ψ k(0)* Gˆ ψ n(0) dv + ε n(1) ∫ψ k(0)*ψ n(0) dv
∑c
m(≠n)
nm [E m( 0 ) − E n( 0 ) ]δ km = −G kn + ε n(1)δ kn
Fihak kiri mempunyai harga jika m=k, sedangkan suku kedua sebelah kanan
sama dengan nol karena k≠n.
( )
c nk Ek( 0) − En( 0) = −Gkn → cnk =
Gkn
En( 0) − Ek( 0)
Gkn
φ n(1) = ∑
k ( ≠n) En − Ek
(0) (0)
ψ k( 0 ) Koreksi order-1 bagi
ψn(o)
(sistem berdegenarasi).
Koreksi order-2
3. ∫ψ n (
( 0)* ˆ ( 0 )
H − En
( 0)
φ )
( 2)
n dv = − ∫ψ n G φ
( 0)* ˆ (1)
n dv + ε ( 2)
n ∫ψ ψ
( 0)* ( 0 )
n n dv + ε (1)
n ∫ φn dv
ψ ( 0 )* (1)
n
∫ {[E }
− En(0) ]ψ n( 0)* φn( 2) dv = − ∑ cnm ∫ψ n( 0)*Gˆ ψ m( 0) dv + ε n( 2)
( 0)
n
m( ≠n )
+ ε n(1) ∑ nm ∫ n ψ m dv
c
m( ≠n)
ψ ( 0 )* ( 0 )
Koreksi
GnmGmn
0 = − ∑ cnmGnm + ε n( 2) → ε n( 2) = ∑ order-2 bagi
m ( ≠ n ) En − E m ψn(o)
(0) ( 0)
m( ≠n)
Gkn
cnk = ( 0)
En − Ek( 0)
Misalkan φn( 2) = ∑ nm m
a
m( ≠n )
ψ ( 0)
anm harus ditentukan
3. ∑ nm
a ˆ
H ( 0)
(
− En
( 0)
ψ ( 0)
m = −G)
ˆ φ (1) + ε ( 2)ψ (0) + ε (1)φ (1)
n n n n n
m( ≠ n )
∑ a ∫ψ (Hˆ
m( ≠n)
nm l
( 0 )* (0)
)
− En( 0) ψ m( 0) dτ = − ∫ψ l( 0)*Gˆ φn(1) dτ
∑a
m(≠n)
nm ( E l
(0)
− E n )δ lm = −
(0)
∑c
m(≠n)
G
nm lm + ε (1)
n ∑c
m(≠n)
nm δ lm
a nl ( El( 0 ) − E n( 0 ) ) = − ∑c
m(≠n)
nm Glm + ε n(1) c nl
G mn Glm G nn G nl
=− ∑ (0) (0) E (0) − E (0)
m(≠n) En − Em
+
n l
Gmn Glm Gnn Gnl
anl = ∑ −
m≠ n ( E n( 0) − E m( 0) )( E n( 0) − El( 0) ) ( E n( 0) − El( 0) ) 2
ψ n = ψ n( 0 ) + φ n(1) + φ n( 2 )
E n = E n( 0 ) + ε n(1) + ε n( 2 )
6.2 Efek Stark
ε 1(1) = eF ∫ψ 1 s r cos θ ψ 1 s dv
∞ π 2π
ao−3
∫e r dr ∫ cosθ sin θ dθ ∫ dϕ = 0
− 2 r / ao
= eF 3
π 0 0 0
Koreksi order-1 terhadap ψ 1s( 0) ψ 2( 0s ) , ψ 2( 0px) , ψ 2( 0py) , ψ 2( 0pz)
E2( 0 )
Gkn
φ n(1) = ∑
k ( ≠n) En − Ek
(0) (0)
ψ k( 0 ) ψ 1s( 0 ) ψ 1(s0) + φ1(s1)
E1( 0 )
φ1(s1) =
eF
E1( 0 ) − E 2( 0 )
[(∫ψ r cosθ ψ dv)ψ + (∫ψ r cosθ ψ dv)ψ
(0)
2s
( 0)
1s
(0)
2s
(0)
2 px
(0)
1s
( 0)
2 px
0,745ao eF
= ψ 2 pz ⎛Z⎞
3/ 2
⎛ Zr ⎞ −Zr / 2ao
E1 − E2
( 0) ( 0)
ψ 2 pz = ψ 210 =
1
⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ e cosθ ;
4 2π ⎝ ao ⎠ ⎝ ao ⎠
3/ 2
1 1 ⎛Z⎞ ⎛ Zr ⎞ −Zr / 2ao
ψ 1s ≡ ψ 100 = ao−3 / 2e −r / ao ; ψ 2 px = ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ e sinθ cosϕ;
π 4 2π ⎝ a o ⎠ a
⎝ o⎠
1 ⎛ r ⎞ 3/ 2
ψ 2s ≡ψ 200 = ao−3 / 2 ⎜⎜ 2 − ⎟⎟ e−r / 2ao ; 1 ⎛Z⎞ ⎛ Zr ⎞ −Zr / 2ao
4 2π ⎝ ao ⎠ ψ 2 py ≡ ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ e sinθ sinϕ.
4 2π ⎝ ao ⎠ a
⎝ o⎠
Koreksi order-2 terhadap E1
( 0)
GnmGmn Gnm
2
ε ( 2)
n = ∑ ( 0) = ∑ (0)
m ( ≠ n ) En − Em m ( ≠ n ) En − E m
( 0) ( 0)
ε 1
(2) e2F 2
= (0)
E 1 − E 2( o )
{[∫ψ (0)
1s r cos θψ (0)
2s dv ] + [∫ψ
2 (0)
1s r cos θψ (0)
2 px dv ] 2
+ [∫ψ (0)
1s r cos θψ (0)
2 py dv ] + [∫ψ
2
(0)
1s r cos θψ (0)
2 pz dv ]}
2
e2 F 2
ε ( 2)
= (0) ( 0, 745 a o ) 2
E1 − E 2( o )
1
( 0,745 a o ) 2 e 2 2
Maka energi yang terkoreksi adalah: E1 = E (0)
− F
E 2( 0 ) − E1( 0 )
1
0,745 a o eF ( 0 )
Fungsi terkoreksi hingga order-1 adalah ψ 1s = ψ 1(s0 ) − ψ 2 pz
E 2( 0 ) − E1( 0 )
ψ 2( 0s ) , ψ 2( 0px) , ψ 2( 0py) , ψ 2( 0pz)
E (0)
2
Harap dihitung sendiri
ψ 1s( 0 )
E1( 0 ) E1 = E1( 0) + ε 1( 2)
ψ 1s = ψ 1(s0) + φ1(s1)