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

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

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’
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 3 / 31

Introduction to spin
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)

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

Introduction to spin
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

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

Introduction to spin
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
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 6 / 31
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

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

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

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

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 )

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

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
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 10 / 31
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

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

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

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 12 / 31
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

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

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)

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

Rotations of orbitals using exponential mappings
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

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

Rotations of orbitals using exponential mappings

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)

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

Rotations of orbitals using exponential mappings
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
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 17 / 31

Rotations of orbitals using exponential mappings

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
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 18 / 31
Rotations of orbitals using exponential mappings
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†

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

Rotations of orbitals using exponential mappings

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
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 20 / 31
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.
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 21 / 31

Rotation of creation-operators
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
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 22 / 31
Rotation of creation-operators

A compact form of ONV with rotated operators

] i = ㆠㆠ· · · ㆠ|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.

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

Rotation of creation-operators
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

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

Rotation of creation-operators
Restrictions on κ̂

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 )
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 25 / 31
p>q

Rotation of creation-operators
Restrictions on κ̂

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.

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 26 / 31

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

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 27 / 31

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

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 28 / 31

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

Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 29 / 31

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)
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 30 / 31
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
Jeppe Olsen (Aarhus) Second Quantization II September 20, 2011 31 / 31