Introduction to Second-quantization I

Jeppe Olsen

Lundbeck Foundation Center for Theoretical Chemistry

Department of Chemistry, University of Aarhus

September 19, 2011

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Contents, lecture I

Brief motivation
Occupation number vectors and the Fock space
Definition of creation operators and the properties
Annihilation operators and their properties
Products of creation and annihilation operators
Summary I
Operators in second quantization
One-electron operators
Two-electron operators
Conclusion and summary

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What is Second Quantization?

The idea
Operators and wavefunctions are described by a common set of
elementary operators (creation and annihilation operators)
Another representation of Quantum Mechanics

Advantages
Antisymmetry is built automatically in
The use of a common set of elementary operators for wavefunctions
and operators allows manipulations not easily realized in the standard
formulation

Disadvantages
Yet another formalism to learn

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Occupation number vectors

Slater-determinants and occupation number vectors

Slater-determinant
A Slater-determinant is an antisymmetric combination of some
spin-orbitals

Occupation number vector (ONV)

Assume a space of M (orthonormal) spin-orbitals are given

An ONV is a vector of M integers, each integer may be 0 or 1

|ki = |k1 , k2 , · · · , kM i, kP = 0, 1 for P = 1, 2, · · · , M

Each occupation number vector gives the occupation of a given

Slater-determinant

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Occupation number vectors
Slater-determinant → ONV

Assume we have a given Slater-determinant, how do we find the

corresponding ONV ?
Entry P in the ONV
1 if spin-orbital P is occupied
0 if spin-orbital P is unoccupied
(The total number of spin-orbitals n must also be known)

Example(M=4)
 

1  φ2 (1) φ4 (1)

Slater-determinant: 2! 
√ 
φ2 (2) φ4 (2) 
ONV: |0, 1, 0, 1i

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Occupation number vectors

Other Examples (still M = 4)

Slater-determinant ONV # of elecs.

φ3 (1) |0, 0, 1, 0i 1
 
 φ (1) φ3 (1) 
√1  1  |1, 0, 1, 0i 2
2!  φ1 (2) φ3 (2) 
 
 φ1 (1) φ3 (1) φ4 (1) 
 
√1  φ (2) φ3 (2) φ4 (2)  |1, 0, 1, 1i 3
3!  1
 φ1 (3) φ3 (3) φ4 (3) 

1 |vaci = |0, 0, 0, 0i 0

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Occupation number vectors
Example: H2 in a minimal basis

Two molecular orbitals and four spinorbitals

MO’s: 1σg , 1σu
Spinorbitals: 1σg α, 1σg β, 1σu α, 1σu β

Groundstate of H+
2
One electron in a 1s-spin-orbital, say 1sα occupied
|1, 0, 0, 0i

Groundstate of H2 (single ONV approximation)

One electron in 1sα, one electron in 1sβ
|1, 1, 0, 0i

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Occupation number vectors

Nomenclature: uses correspondence between ONV and SD

kP is occupation number for spin-orbital P
If kP = 1, spin-orbital/level P is occupied
If kP = 0, spin-orbital/level P is unoccupied
P
P=1,M kP is the total number of electrons in the ONV
The ONV with zero electrons is the vacuum state |vaci = |0, 0, · · · , 0i

ONV’s represents SD’s, but are not SD’s

We have a one-to-one mapping between ONV’s and SD’s
But they are not identical
SD’s are functions of space-coordinates of electrons
In SD’s there is explicit reference to electron 1, electron 2, ...
ONV’s a just vectors in an abstract vector space

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Occupation number vectors
In other words

This place is to small for two of us / John Wayne

To be or not to be, that is the question / Hamlet

I am you and you are me / John Lennon

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The Fock-space

Basic definitions
Defined by the total number of spin-orbitals, M
Abstract vector space
The ONV’s are unit-vectors
Each unit-vector corresponds thus to
P a SD, combination of several
determinants corresponds to |ci = k ck |ki
Contains ONV’s with 0,1,... M electrons
We thus map SD’s in real Cartesian space to ONV’s in the
Fock-space.

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The Fock-space

Inner product between ONV’s

We will define an inner product between ONV’s, so it includes the
standard inner product of SD’s for orthonormal orbitals
M
Y
hk|mi = δk,m = δkP ,mP
P=1

= 1 if the two ONV’s are identical

= 0 if the two ONV’s differ in one or more occupation
numbers
Inner product also defined for ONV’s with different number of
electrons

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Creation-operators aP†
Definition
One creation operator aP† for each spin-orbital P

aP† |k1 , · · · , 0P , · · · , kM i = ΓkP |k1 , · · · , 1P , · · · , kM i

aP† |k1 , · · · , 1P , · · · , kM i = 0
PP−1
( kQ )
ΓkP = (−1) Q=1

Comments
Creates an electron in spin-orbital P if this spin-orbital is unoccupied
in |ki
Gives zero if spin-orbital P is occupied in |ki
Phase-factor ΓkP
count the number of electrons in |ki before P
Even number → ΓkP = 1, odd → ΓkP = −1
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Creation-operators aP†

Examples, M=4
1 a1† |1, 0, 0, 0i = 0
2 a1† |0, 1, 0, 0i = |1, 1, 0, 0i
3 a2† |1, 0, 0, 0i = −|1, 1, 0, 0i

All ONV’s may be obtained from |vaci

Y
|k1 , k2 , · · · , kM i = (ap† )kp |vaci
P=1,M

(Â)0 = 1̂

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Creation-operators aP†
Example: H2 in a minimal basis

Two molecular orbitals and four spinorbitals

Spinorbitals: 1σg α, 1σg β, 1σu α, 1σu β

Four creation operators (M = 4)

† † † †
1: a1σ gα
, 2: a 1σg β , 3: a 1σu α , 4: a1σu β

Groundstate of H+
2
†
|1, 0, 0, 0i = a1σgα
|vaci

Groundstate of H2
† †
|1, 1, 0, 0i = a1σ a
g α 1σg β
|vaci

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Creation-operators aP†
Products of two creation-operators

aP† aP†
Consider the action of aP† aP† on an arbitrary ONV, two cases
1 aP† aP† | · · · , 1P , · · ·i = aP† 0 = 0
2 aP† aP† | · · · , 0P , · · ·i = ΓkP aP† | · · · , 1P , · · ·i = 0
aP† aP† working on any ONV gives 0, so

aP† aP† = 0

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Creation-operators aP†
Products of two creation-operators

†
aP† aQ † †
and aQ aP , P < Q

Only non vanishing if both spin-orbitals P, Q are unoccupied

aP† aQ
†
| · · · 0P · · · 0Q · · ·i = ΓkQ aP† | · · · 0P · · · 1Q · · ·i
= Γ(k)P Γ(k)Q | · · · 1P · · · 1Q · · ·i
† † †
aQ aP | · · · 0P · · · 0Q · · ·i = ΓkP aQ | · · · 1P · · · 0Q · · ·i
= −ΓkP ΓkQ | · · · 1P · · · 1Q · · ·i (1)
so (aP† aQ
†
+ † †
aQ aP )| · · · 0P · · · 0Q · · ·i = 0
Same relation holds(trivially) for other ONV’S so

aP† aQ
† † †
+ aQ aP = 0

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Creation-operators aP†
Products of two creation-operators

Conclusion: aP† aQ
† † †
+ aQ aP = 0

holds for all P, Q

Creation-operators anti commute
The anti-commutation arise from the definition of the phase-factor Γ
Also written as [aP† , aQ
†
]+ = 0
([A, B]+ = AB + BA)

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Annihilation-operators aP
Definition
The operators obtained by conjugating aP† : aP = (aP† )†

Properties
From the definition of the creation-operators it may be shown

aP | · · · 1P · · ·i = ΓkP | · · · 0P · · ·i
aP | · · · 0P · · ·i = 0 (2)
1 aP annihilates an electron in spin-orbital P if possible
Examples
a1 |0, 0, 0, 0i = 0
a1 |1, 1, 0, 0i = |0, 1, 0, 0i
a2 |1, 1, 0, 0i = −|1, 0, 0, 0i
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Annihilation-operators aP
Products

Product of two annihilation operators

From the anti-commutation of the creation operators
aP† aQ
† † †
+ aQ aP = 0
We obtain by conjugation

(aP† aQ
† † † †
+ aQ aP ) =
aQ aP + aP aQ =0 (3)

Thus annihilation-operators are also anti-commuting [aP , aQ ]+ = 0

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Products of operators

Anti-commutation of creation- and annihilation-operator

aP† aQ + aQ aP† = ?
From examining the action on various ONV’s one obtains
1 P=6 Q : aP† aQ + aQ aP† = 0
2 P = Q : aP† aP + aP aP† = 1
Collecting the two gives aP† aQ + aQ aP† = δPQ
δPQ is the Kronecker delta-function

1 for P = Q
δPQ =
6 Q
0 for P =

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Products of operators
The operator aP† aP

Two cases

aP† aP | · · · 1P · · ·i = ΓkP aP† | · · · 0P · · ·i

= (ΓnP )2 | · · · 1P · · ·i = | · · · 1P · · ·i
aP† aP | · · · 0P · · ·i = 0

Combined expression
aP† aP | · · · kP · · ·i = kP | · · · kP · · ·i
When aP† aP works on a ONV, it thus gives the ONV multiplied with
the occupation number
N̂P = aP† aP is thus the number-operator for spin-orbital P
P P
N̂ = P N̂P gives the total number of electrons, P kP of an ONV
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Products of operators
Excitation-operators

Definition of one-electron excitation operator

X̂QP = aP† aQ (P 6= Q)

Comments
aP† aQ | · · · 0P · · · 1Q · · ·i = ±| · · · 1P · · · 0Q · · ·i
Removes one electron in spin-orbital Q and creates one electron P
In other words: Excites one electron from Q to P
aP† aQ (P 6= Q) is therefore a single-electron excitation
Two-electron excitations may be obtained as aP† aQ
†
aR aS

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Elements of second quantization

Basis vectors |ki = |k1 ,Q k2 , · · · , kM i, kP = 0, 1

Inner product hk|mi = nP=1 δkP mP
Creation operators aP† |k1 , · · · , 0P , · · · , kM i = ΓkP |k1 , · · · , 1P , · · · , kM i
P
( P−1
ΓP = −1 Q=1 kQ )
k

aP† |k1 , · · · , 1P , · · ·, kP i = 0
Annihilation operators aP |k1 , · · · , 1P , · · · , kM i = ΓkP |k1 , · · · , 0P , · · · , kM i
aP |k1 , · · · , 0P , · · · , kM i = 0
Anti-commutation aP† aQ + aQ aP† = δPQ
relations aP† aQ
†
+ aQ † †
aP = 0
aP aQ + aQ aP = 0
Number operators aP† aP |ki = kP |ki
P P
( P aP† aP )|ki = ( P kP )|ki
Vacuum state |vaci = |01 , 02 , · · · , 0M i
hvac|vaci = 1
aP |vaci = 0
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Operators in second quantization

The problem
In the Fock-space, we could define very simple operators like the
number-operator
We need representations of quantum mechanical operators, for
example the kinetic-energy operator

Procedure
1 We know the mapping |SDi i → |ONVi i
2 We know the mapping |SDj i → |ONVj i
3 Obtain the second quantization representation, fˆ of a given
first-quantization operator f c by requiring
hONVi |fˆ|ONVj i = hSDi |f c |SDj i

It is only then we have obtained an alternative representation of

quantum mechanics
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Operators in second quantization
One-electron operators

Examples
kinetic energy operator, nuclear-electron attraction operator

First-quantization form
P
Form: =fc i=1,N f c (xi ), N: number of electrons
Properties:
1 Works on SD’s with at least one electron
2 Connects Slater-determinants differing in at most one set of
occupations

Implies form of second quantization operator

P †
fˆ = PQ fPQ aP aQ where fPQ pt are unknowns

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Operators in second quantization

One-electron operators

fPQ =?
R
Setting fPQ = dx φP (x)? f c (x)φQ (x) gives the same
matrix-elements in first- and second quantization
Example: Diagonal elements
First quantizationP(from Relementary QM)
hSDk |f c |SDk i = P kP dx φP (x)? f c (x)φP (x)
Second quantization:
X
hk| fPQ aP† aQ |ki =
PQ
X X
hk| fPP aP† aP |ki = hk| fPP N̂P |ki
P P
X Z
= kP dx φP (x)? f c (x)φP (x)
P

The phase-factor Γk is essential for agreement

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Operators in second quantization
Example: one-electron operator in the H2 minimal basis

The operator

† †
ĥ = h1σg α1σg α a1σ g α a 1σg α + h 1σg β1σ g β a 1σ a
g β 1σg β
† †
+ h1σu α1σu α a1σu α a1σu α + h1σ u β1σu β a 1σ a
u β 1σu β

Integrals between 1σg , 1σu vanish by symmetry

Integrals between α and β vanish as hc does no change spin

Some matrix elements

†
hvac|a1σg β a1σg α ĥ a1σ a† |vaci = h1σg α1σg α + h1σg β1σg β
g α 1σg β

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Operators in second quantization

Two-electron operators

Examples
Electron-electron repulsion, two-electron spin-orbit

First-quantization form
1 P0
Form: g c = 2 i,j=1,N g c (i, j),
Properties:
1 Works on SD’s with at least two electron
2 Connects Slater-determinants differing in at most two sets of
occupations

Implies form of second quantization operator

P
ĝ = 1
2 PQRS gPQRS aP† aR† aS aQ where gPQRS pt are unknowns

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Operators in second quantization
Two-electron operators

gPQRS =?
Equivalence is obtained between first and second quantization by
setting
Z
gPQRS = dxdx0 φ?P (x)φ?R (x0 )g c (x, x0 )φQ (x)φS (x0 )

Shown by going through the various cases

The phase-factor Γk is essential for obtaining agreement

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Operators in second quantization

The Hamiltonian in SQ

In spin-orbital form
X 1 X
Ĥ = hPQ aP† aQ + gPQRS aP† aR† aS aQ + hnuc
2
PQ PQRS

P
PQ hPQ aP† aQ contains kinetic energy and electron-nuclear
attraction
1 P † †
2 PQRS g PQRS aP aR aS aQ is electron-electron repulsion
The Hamiltonian is a weighted sum of single and double excitations
Simplifications when we consider orbitals ( instead of spin-orbitals)

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Conclusion

We have now
Obtained a new way of representing antisymmetric wave-functions
Obtained a new way of representing operators

So that
Expectation values are identical to the standard formulation

In other words
We have obtained a new representation of quantum mechanics for
electrons

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Operators in first and second quantization

First quantization Second quantization

One-electron operator One-electron operator

P P †
i f (xi ) PQ fPQ a P aQ

Two-electron operator Two-electron operator

1P 1P † †
2 i6=j g (xi , xj ) 2 PQRS gPQRS aP aR aS aQ

Operators are independent Operators depend on

of spin-orbital basis spin-orbital basis

Operators depend in Operators are independent

the number of electrons of the number of electrons

Exact operators Projected operators

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