Tips Operators
Tips Operators
Tips Operators
October 21
Second quantization
Evaluation of one and twotwo-particle matrix elements
Coulomb matrix elements: example of twotwo-particle
operator (second quantization form)
Helium atom: LS coupled states
Second quantization
1
2
Second quantization:
atomic electrons (fermions)
One-electron state |k>
Described by the wave function k(ri)
k = ak 0
Creation operator
0 0 =1
Vacuum state
(no electrons)
Second quantization:
atomic electrons (fermions)
One-electron state |k>
Described by the wave function k(qi)
k = ak 0
k = 0 ak
ak 0 = 0 :
Vacuum state
(no electrons)
Creation operator
0 0 =1
Annihilation operator
there are no electrons to annihilate in a vacuum
0 ak = 0
Anticommutation relations
{a , a } = a a
{a , a } = a a
{a , a } = a a
i j
+ a j ai = 0
+ a j ai = 0
+ a j ai = ij
ak 0 = 0
0 ak = 0
i j = 0 ai a j 0 = 0 ij a j ai 0 = ij
Two-electron states
First quantizaiton:
quantizaiton:
Slater determinant
jk (q1 , q2 ) =
Second quantizaiton
1 j (q1 ) k (q2 )
2 j (q2 ) k (q2 )
jk = a j ak 0
ij ( q1 , q2 ) kl ( q1 , q2 ) = ik jl il jk
ij kl = 0 a j ai ak al 0
NOTE: reversed order
Need to evaluate
a j ai ak al
Creation operators
left
to normal form
form:
Annihilation operators
right
a j ai ak al = a j al ik a j ak ai al = ik jl al a j ik jk ai al + ak a j ai al
= ik jl al a j ik jk il + jk al ai + ak a j il ak a j al ai =
= ik jl al a j ik jk il + jk al ai + ak a j il jl ak ai + ak al a j ai
Creation operators
left
Annihilaiton operators
right
a j ai ak al = a j al ik a j ak ai al = ik jl al a j ik jk ai al + ak a j ai al
= ik jl al a j ik jk il + jk al ai + ak a j il ak a j al ai =
= ik jl al a j ik jk il + jk al ai + ak a j il jl ak ai + ak al a j ai
ij kl = 0 a j ai ak al 0
a j ai ak al = ik jl al a j ik jk il + jk al ai + ak a j il jl ak ai + ak al a j ai
0
0 a a a a 0 = ik jl 0 a a j 0 ik jk il + jk 0 a a 0
j i k l
l i
+ 0 a a j 0 il jl 0 a a 0 + 0 a a a j ai 0
k i
k l
= ik jl jk il
Exactly the result we had in first quantization
Many-particle operators in
second quantization
ai 0
one-particle state
two-particle state
States ai a j 0
ai a j
an 0
N-particle state
described
by Slater determinants
in first quantization
Operators
First quantizaiton
One-particle
operator
Two-particle
operator
F=
N
i =1
G=
f (ri )
1
g (rij )
2 i j
Second quantizaiton
F=
fij ai a j
i, j
G=
1
2
gijkl ai a j al ak
i, j
gijkl = g jilk
Many-particle operators in
second quantization
First and second quantization description must produce identical
results; however, is it more convenient to use second quantization
quantization
for calculation of properties of manyelectro
systems
as the
many
antisymmetrization properties are carried by the operators rather
than the wave functions as in the case of Slater determinants.
F=
G=
fij ai a j
i, j
1
2
gijkl ai a j al ak
i, j
f ab = a f b = d 3 r a (r ) f (r ) b (r )
g abcd = ab g cd = d 3 r1 d 3 r2 a (r1 ) b (r2 ) g (r12 ) c (r1 ) d (r2 )
The rules for calculating matrix elements are equivalent, for example:
ab G ab =
1
2
H0 =
Second quantizaiton
N
i =1
H0 =
hi
1
Z
hi = i2
2
ri
N
i =1
i ai ai
eigenvalue of hi
H'=
1
r12
H'=
1
2
gijkl ai a j al ak
ijkl
1
c (r1 ) d (r2 )
r12
N
i =1
i ai ai
H 0 ab = ( a + b ) ab
However, it is not necessarily an angular momentum eigenstate.
Lets construct eigenstates of {H, L2, Lz, S2,Sz } from |ab> states.
L = l a + lb
S = sa + sb
S=0: singlet state
S=1: triplet states
S=0,1
He-like systems:
construction of coupled states
ab = aa ab 0
Therefore, the coupled states are given by the sum over magnetic
moments which contains two Clebsch-Gordon coefficients:
a
lama
ab, LM L , SM S =
ma mb a b
LML
SMS
aa ab 0
lbmb
Normalization factor
1
1
2
na nb , la lb
Identical orbitals na = nb , la = lb
He-like systems:
First-order energy
a
lama
ab, LM L , SM S =
ma mb a b
LML
SMS
aa ab 0
lbmb
H'=
1
2
gijkl ai a j al ak
ijkl
1
c (r1 ) d (r2 )
r12
1
c (r1 ) d (r2 )
r12
1
4 r<k k *
Ykq (1 , 1 )Ykq ( 2 , 2 )
=
r12 k =0 2k + 1 r>k +1 q = k
Cqk (r) =
4
Ykq ( , )
(2k + 1)
1
1
r<k k
=
=
(1) q Cqk (r1 ) Ckq (r2 )
r12 r1 r2 k =0 r>k +1 q = k
r<k k
1
=
(1) q Cqk (r1 ) Ckq (r2 )
r12 k =0 r>k +1 q = k
k =0
1
c (r1 ) d (r2 )
r12
r<k
Rn l (r1 ) Rnd ld (r2 )
r>k +1 c c
radial
integral
d 1Yla ma (1 , 1 ) C kq (1 , 1 )Ylc mc (1 , 1 )
la ma C kq lc mc
d 2Ylb mb ( 2 , 2 ) C k q ( 2 , 2 )Yld md ( 2 , 2 )
lb mb C k q ld md
(1) q
q = k
g abcd =
k =0
Rk (abcd )
q = k
(1)q la ma C kq lc mc lb mb C k q ld md
g abcd =
k =0
Rk (abcd )
q = k
lama
(1)q
kq
lcmc
lbmb
We use
k -q
ldmd
lbmb
k -q
la C k lc lb C k ld
ldmd
lbmb
= (1)k q
kq
ldmd
lbmb
lama
k =0
Rk (abcd )
(1) k
q = k
la C k lc lb C k ld
kq
kq
ldmd
lcmc
lama
k =0
(1) k Rk (abcd ) la C k lc lb C k ld
lbmb
k
lcmc
ldmd
X k (abcd )
lama
g abcd =
lbmb
k =0
lcmc
X k (abcd )
ldmd
g abcd =
lbmb
k =0
lcmc
X k (abcd )
ldmd
r<k
Rn l (r1 ) Rnd ld (r2 )
r>k +1 c c
l1 k l2
0 0
10
lama
ab, LM L , SM S =
LML
ma mb a b
SMS
aa ab 0
Assume
la=la
lb=lb
lbmb
lama
=2
LML
H'=
1
2
SMS
lbmb
lama
lbmb
gijkl ai a j al ak ;
LML
SMS
b
ab G ab = g abab g abba
ijkl
a a ' b b '
= (2S + 1)
SMS
SMS
b
SMS
SMS
b
=1
j3m3
1
j ' j m 'm
2 j3 +1 3 3 3 3
j2
11
Term 2 :
a b a ' b '
a b ' b a '
SMS
SMS
= (2S + 1)(1)
SMS
S +1
SMS
= (1)
E (1) = 2
ma 'mb ' ma mb
lama
LML
lbmb
lama
Assume
la=la
lb=lb
LML
lbmb
lama
lbmb
k
lama
X k (abab) + (1)S
+
k
lbmb
lbmb
lbmb
X k (abba ) )
lama
g abcd =
lbmb
k =0
lcmc
X k (abcd )
ldmd
12
lama
LML
ma 'mb ' ma mb
LML
lbmb
lama
lama
lbmb
lb
la
la
lb
lbmb
rotate
to the right
LML
lama
lbmb
+
k
lama
lbmb
lbmb
lbmb
lama
=(2L+1)
lama
lbmb
L
k
lama
LML
ma 'mb ' ma mb
lbmb
la
la
lb
lb
lama
LML
lbmb
lbmb
k
lbmb
lama
L
k
13
ab, LM L , SM S
Final expression:
First order energy for He-like system
E (1) = 2
la
lb
lb
la
X k (abab)
la
lb
la
lb
X k (abba)
r<k
Rn l (r1 ) Rnd ld (r2 )
r>k +1 c c
l1 k l2
0 0
0 0 0
0 0 0
=1
14