Introduction To Second-Quantization II

Introduction to Second-quantization II
Jeppe Olsen
Lundbeck Foundation Center for Theoretical Chemistry

Department of Chemistry, Aarhus
September 20, 2011
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 1 / 31
Contents, lecture II
Spin in second quantization Form of spin-free one- and two-electron

operators, section 9, 79-83
Rotations using exponentials I: first quantization, section 8
Rotations using exponentials II: second quantization, section 8
Density matrices - bonus slides

Introduction to spin
Spin-functions for one electron, first quantization
Two spin-functions, α(ms ), β(ms )

ms can take the two values 12 , − 12
α( 21 ) = 1, α(− 12 ) = 0
β( 21 ) = 0, β(− 12 ) = 1
Spin properties
1 3
Sz α = α S 2 α = α
2 4
1 3
Sz β = − β S 2 β = β
2 4
α is ’spin-up’, β is ’spin-down’
Spin-functions for one electron, first quantization, cont’d
Integration over spin

R
Easy: dms f (ms ) = f ( 12 ) + f (− 12 )
α, β constitute an orthonormal basis
R ?
R
1
R dm s α (m s )α(m s ) = dms β ? (ms )β(ms ) = 1
2 dms α? (ms )β(ms ) = 0
(easily checked from definitions)

Spin orbitals in first and second quantization
First quantization: separate functions for spatial- and spin-parts, e.g.

φp (r)α(ms )
Second quantization: Both spatial and spin-parts created by one
†
operator for example apα
† †
Ground state of H2 : a1σg α a1σ gβ
|vaci
Anti-commutation relation
†
[apσ , aqτ ]+ = δpq δστ
Various types of operators
Spin-free operators
Operator that does not change spin-functions
f c α = αf c f c β = βf c
Operators like kinetic energy and Coulomb-repulsion depend only on

spatial coordinates → spin-free
Pure spin-operators
Operators that does not change spatial functions
f c φp (r) = φp (r)f c
Operators like S+ , S− , S 2 are of this type
Mixed operators
Changes both spatial and spin functions
Pure spin-operators
Example: S+
Form X
†
S+ = (S+ )pσqτ apσ aqτ
pσqτ
S+ in FQ
S+ β = α S+ α = 0
S+ φp = φp S+ (S+ is pure spin-operator)
The integrals (S+ )pσqτ

Z Z
(S+ )pσqτ = dr dms φp (r)? σ(ms )? S+ (ms )φq (r)τ (ms )
Z Z
= dr φp (r)? φq (r) dms σ(ms )? S+ (ms )τ (ms ) = δpq δσα δτ β
Pure spin-operators
Example: S+
From last slide

(S+ )pσqτ = δpq δσα δτ β
So
X
†
S+ = (S+ )pσqτ apσ aqτ
pσqτ
X
†
= δpq δσα δτ β apσ aqτ
pσqτ
X
†
= apα apβ
p
Corresponds to the intuitive picture: changes β to α

Spin-free operators
One-electron operators
Do you remember: general form for one-electron operator

X
ĥ = hPQ aP† aQ
PQ
Z
hPQ = dx φ?P (x) h(x) φQ (x)
Separation of spatial and spin parts

P → pσ, Q → qτ
X
†
ĥ = hpσqτ apσ aqτ
pσqτ
Z Z
hpσqτ = dr dms φ?p (r)σ ? (ms ) h(r, ms ) φq (r)τ (ms )
Spin-free operators
One-electron operator
The integrals hpσqτ

Z Z
hpσqτ = dr dms φ?p (r)σ ? (ms )h(r)φq (r)τ (ms )
Z Z
= dms σ ? (ms )τ (ms ) dr φ?p (r)h(r)φq (r) = δστ hpq
P † † †
Introduce Epq = a a
σ pσ qσ = a a
pα qα + a pβ aqβ
(generator of the linear group)
The operator then become

P † P
ĥ = pσqτ δστ hpq apσ aqτ = pq hpq Epq
hpq depends only on orbitals
Spin-free operators
Two-electron operator
General two-electron operator in SQ

1 X
† †
ĝ = gpσ,qτ,r µ,sν apσ ar µ asν aqτ
2 pσ,qτ,r µ,sν
Simplification for spin-free two-electron operator
gpσ,qτ,r µ,sν = gpqrs δστ δµν

Z
gpqrs = drdr0 φ?p (r)φ?r (r0 )g c (r, r0 )φq (r)φs (r0 )
Gives spin-free two-electron operator

1X X
† †
ĝ = gpqrs ( apσ ar τ asτ aqσ )
2 pqrs στ
Spin-free operators
Two-electron operator, cont’d
A simple rewrite to obtain E-operators

1X X
† †
ĝ = gpqrs ( apσ ar τ asτ aqσ )
2 pqrs στ
1X X
† †
=− gpqrs ( apσ ar τ aqσ asτ )
2 pqrs στ
1X X
†
=− gpqrs ( apσ (−aqσ ar†τ + δqr δστ )asτ )
2 pqrs στ
1X X
† †
X
†
= gpqrs ( apσ aqσ ar τ asτ − δqr apσ asσ )
2 pqrs στ σ
1X 1X
= gpqrs (Epq Ers − δqr Eps ) = gpqrs epqrs
2 pqrs 2 pqrs
Definition: epqrs = Epq Ers − δqr Eps

Spin-free operators
The nonrelativistic Hamiltonian
Terms
One-electron part containing kinetic energy and nuclear attraction ←
ĥ
Two-electron part containing electron-electron repulsion ← ĝ
Spin-free !
The form
Ĥ = ĥ + ĝ
X 1X
= hpq Epq + gpqrs (Epq Ers − δqr Eps )
pq
2 pqrs
X 1X
= hpq Epq + gpqrs epqrs
pq
2 pqrs
Rotations of orbitals using exponential mappings
Problem
A set of orthonormal spin-orbitals is given φ
Obtain all orthonormal spin-orbitals φ̃ that can be obtained as linear
combinations of φ
φ̃ = φU
hφ̃P |φ̃Q i = δPQ
We want a simple parameterization of all orthonormal spin-orbitals φ̃

Occurs in SCF and MCSCF optimization
( Note: P, Q now refers to spin-orbitals)

May the elements of U be used as independent parameters?
No, because:
The required orthonormality of φ̃ requires that U is unitary
U† U = 1
The unitary conditions on U gives constraints on its elements

The elements of U can therefore not be used as independent
parameters
A parameterization of unitary matrices may be obtained in terms of

exponential matrices

Exponential matrices
Definition
∞
X 1 n
exp(A) = A
n!
n=0
1
= 1 + A + A2 + · · ·
2
Straightforward extension of Taylor-expansion of exp(x), where x is a

number
Converges for any choice of finite A ( assuming finite dimension)

Exponential matrices, cont’d
Relations
exp(A) exp(−A) = 1
exp (A)† = exp(A† )
B exp(A)B−1 = exp(BAB−1 )
exp(A + B) = exp(A) exp(B) iff [A, B] = 0
The Baker-Campbell-Hausdorf (BCH) expansion
1
exp(A)B exp(−A) = B + [A, B] + [A, [A, B]]
2
1
+ · · · + [A, [A, · · · , [A, B] · · · ]] + · · ·
n! | {z }
n

Unitary matrices as exponentials of antihermitian matrices
Any unitary matrix may be written as the exponential of an

antihermitian matrix
U = exp(−κ) κ† = −κ(κ is antihermitian, USED HERE)

U = exp(iκ) κ† = κ(κ is hermitian)
Relies on two theorems

1 exp(−κ) is unitary for κ antihermitian
2 All unitary matrices can be written in this form
1: exp(−κ) is unitary
exp(−κ)† exp(−κ) = exp(κ) exp(−κ)

=1
Unitary matrices as exponentials of antihermitian matrices, cont’d
2: All unitary matrices may be written as exp(−κ)

A unitary matrix U may be diagonalized U = VV† , VV† = 1
is a complex diagonal matrix and |i | = 1
|i | = 1 → i = exp(iδi ), δi is real
Therefore U = V exp(iδ)V† = exp(−(−iVδV† ))
−iVδV† is antihermitian, (−iVδV† )† = iVδV†

Unitary matrices as exponentials of antihermitian matrices, cont’d
What is so great about U = exp(−κ)

It as easy to obtain a independent set of parameters for an
antihermitian matrix
1 Elements at or below the diagonal are independent parameters
2 Obtain the elements above the diagonal as κQP = −κ?PQ , P > Q
A parameterization of all sets of orthonormal orbitals

φ̃ ← U ← κ ← κPQ , P > Q
The energy as a function of orbitals

E = E (φ̃) = E (κlow ), for example the SCF energy
The energy is now a function of a set of independent parameters
Standard methods like Newton method may be used to optimize E
Of some use for HF, essential for MCSCF
Rotation of creation-operators
Rotation of orbitals → rotation of creation operators
P
Rotated orbitals: φ̃P = Q φQ UQP , U = exp(−κ)
A creation
P operator creating on electron in spin-orbital φ̃P :
† †
ãP = Q aQ UQP
An ONV of rotatedPspin-orbitals
ãP† 1 ãP† 2 · · · |vaci = Q1 Q2 ··· aQ
† †
a · · · |vaciUQ1 P1 UQ2 P2 · · ·
1 Q2
Complicated form
An operator form of ã†

P
ãP† = Q
†
aQ (exp(−κ))QP
We will show that ãP† = exp(−κ̂)aP† exp(κ̂)
P
κ̂ = PQ κPQ aP† aQ (κ̂ is an antihermitian one-electron operator)
The exponential of an operator is defined as the exponential of matrix
and has the same properties and relations.
P
exp(−κ̂)aP† exp(κ̂) = Q
†
exp(−κ)QP aQ
The BCH expansion gives
1
exp(−κ̂)aP† exp(κ̂) = aP† + [aP† , κ̂] + [[aP† , κ̂], κ̂] + · · ·
2
Calculating the commutator gives
exp(−κ̂)aP† exp(κ̂)
†
X †
X 1 †
= aP − κQP aQ + (κ)2QP aQ + ···
2!
Q Q
X † 1
= aQ (1 − κ + (κ)2 + · · · )QP
2!
Q
X †
= exp(−κ)QP aQ
Q
A compact form of ONV with rotated operators
] i = ã† ã† · · · ã† |vaci

|ONV P1 P2 PN
= exp(−κ̂)aP† 1 exp(κ̂) exp(−κ̂)aP† 2 exp(κ̂)

· · · exp(−κ̂)aP† N exp(κ̂)|vaci
= exp(−κ̂)aP† 1 aP† 2 · · · aP† N |vaci
= exp(−κ̂)|ONV i
] i = exp(−κ̂)|ONV i
|ONV
Applying a single exponential operator rotates all the spin-orbitals , used
for generating all sets of orthonormal orbitals in SCF and MCSCF.
Restrictions on κ̂
Hitherto: unrestricted κ̂
P
κ̂ = PQ κPQ aP† aQ with κ general antihermitian matrix → complete
general spin-orbital transformation
1 Allows the spin-orbitals to become complex (elements of κ may be
complex)
2 α- and β-spin-orbitals are allowed to have different spatial parts
3 α- and β-spin-orbitals are allowed to mix
Two types of restrictions

1 Restrict rotations to allow only real orbitals
2 Restrict rotations to ensure that spatial parts of α− and
β-spin-orbitals are identical

Restriction to real orbitals

Restrict κ to R κ containing only real elements
Rκ is an antisymmetric matrix, R κQP = −R κPQ , R κPP = 0
X †
X †
X
κ̂ = R
κPQ aP aQ = R
κPQ aP aQ + R
κPQ aP† aQ
PQ P>Q P<Q
X X X
= R
κPQ aP† aQ + R †
κQP aQ aP = R
κPQ (aP† aQ − aQ
†
aP )
P>Q P>Q P>Q
Restrictions on spin-orbitals
Rκ = R κpβqα = 0 (no mixing of α,β-orbitals)
pαqβ
Rκ = R κpβqβ = R κpq (identical rotations of α,β-orbitals)
pαqα
X † †
R † †
κ̂ = κpq (apα aqα + apβ aqβ − aqα apα − aqβ apβ )
p>q
X
R
= κpq (Epq − Eqp )
p>q
Real and spin-conserving rotations of ONV
] i = exp(−κ̂)|ONV i
|ONV
X
R
= exp(− κpq (Epq − Eqp ))|ONV i
p>q
This is the form that will be used in the MCSCF lectures -with small
notational differences.

Density matrices
One-electron orbital density matrix
A wave function and a spinfree 1-e-operator

X X
|0i = Ck |ki Ω = Ωpq Epq
k pq
Expectation value of spin-free 1-e operator

X
h0|Ω̂|0i = Ωpq h0|Epq |0i
pq
Consists of two parts

Integrals Ωpq : Depends on actual operator, independent of C
Matrix-elements h0|Epq |0i: Independent of operator, depends on C
Density matrices
One-electron orbital density matrix, cont’d
From last slide

P
h0|Ω̂|0i = pq Ωpq h0|Epq |0i
The one-electron orbital density matrix, D

Dpq = h0|Epq |0i
Matrix with dimensions M by M
All the information about C needed to calculate expectation values of
spin-free one-electron operators
Data reduction: million/billion of parameters in C → M by M matrix
Diagonalization of D → natural orbitals

Density matrices
Natural orbitals
Deinition
The density matrix D is Hermitian
And may therefore be diagonalized
The eigenvalues of D are the natural occupation nummbers
The eigenvectors defines the natural orbitals
Natural occupation numbers

Gives occupation of the natural orbitals in the wave function
Are between 0 and 2
Assist in the analysis of wave functions
Density matrices
The density in real space
Expectation value of one-electron multiplicative operator
XZ
h0|Ω̂|0i = dr φ?p (r)Ωc (r)φq (r) Dpq
pq
Z ! Z
X
= dr Ωc (r) Dpq φ?p (r)φq (r) = dr Ω̂c (r)ρ(r)
pq
P
The density ρ = pq Dpq φ?p (r)φq (r)
Function in real space, function of coordinates of one electron
Sufficient to evaluate expectation values of multiplicative
1-electron-operators
Of importance for DFT...
(The density matrix D allows the calculation of expectation values of
all one-electron operators)
Density matrices
Two-electron orbital density matrix
A wave function and a spinfree 2-e-operator

X 1X
|0i = Ck |ki Ω= Ωpqrs epqrs
2 pqrs
k
Expectation value of spin-free 2-e-operator
1X 1X
h0|Ω̂|0i = Ωpqrs h0|epqrs |0i = Ωpqrs dpqrs
2 pqrs 2 pqrs
d is the 2-e orbital density matrix
Contains all information about C needed to calculate expectation
values of spin-free 2-electron operators
Dimension M 4
Cannot be explicitly constructed and stored for large molecules
Is therefore usually constructed on the flight when needed

Introduction To Second-Quantization II

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Introduction to Second-quantization II

Lundbeck Foundation Center for Theoretical Chemistry

September 20, 2011

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 1 / 31

Spin in second quantization Form of spin-free one- and two-electron

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 2 / 31

Two spin-functions, α(ms ), β(ms )

Integration over spin

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 4 / 31

First quantization: separate functions for spatial- and spin-parts, e.g.

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 5 / 31

Operators like kinetic energy and Coulomb-repulsion depend only on

Operators like S+ , S− , S 2 are of this type

The integrals (S+ )pσqτ

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 7 / 31

From last slide

Corresponds to the intuitive picture: changes β to α

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 8 / 31

Do you remember: general form for one-electron operator

Separation of spatial and spin parts

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 9 / 31

The integrals hpσqτ

(generator of the linear group)

The operator then become

General two-electron operator in SQ

Simplification for spin-free two-electron operator

gpσ,qτ,r µ,sν = gpqrs δστ δµν

Gives spin-free two-electron operator

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 11 / 31

A simple rewrite to obtain E-operators

Definition: epqrs = Epq Ers − δqr Eps

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 13 / 31

Rotations of orbitals using exponential mappings

We want a simple parameterization of all orthonormal spin-orbitals φ̃

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 14 / 31

The unitary conditions on U gives constraints on its elements

A parameterization of unitary matrices may be obtained in terms of

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 15 / 31

Rotations of orbitals using exponential mappings

Straightforward extension of Taylor-expansion of exp(x), where x is a

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 16 / 31

The Baker-Campbell-Hausdorf (BCH) expansion

Rotations of orbitals using exponential mappings

Any unitary matrix may be written as the exponential of an

U = exp(−κ) κ† = −κ(κ is antihermitian, USED HERE)

Relies on two theorems

exp(−κ)† exp(−κ) = exp(κ) exp(−κ)

2: All unitary matrices may be written as exp(−κ)

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 19 / 31

Rotations of orbitals using exponential mappings

What is so great about U = exp(−κ)

A parameterization of all sets of orthonormal orbitals

The energy as a function of orbitals

An operator form of ã†

The BCH expansion gives

Calculating the commutator gives

A compact form of ONV with rotated operators

] i = ã† ã† · · · ã† |vaci

= exp(−κ̂)aP† 1 exp(κ̂) exp(−κ̂)aP† 2 exp(κ̂)

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 23 / 31

Two types of restrictions

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 24 / 31