Modern Quantum Chemistry — Szabó & Ostlund

Chapter 2 · Many-Electron Wave Functions and Operators

Detailed lecture notes with full derivations

Preface
Chapter 2 of Szabó & Ostlund is the conceptual heart of the book. Chapter 1 has introduced the
clamped-nuclei (Born–Oppenheimer) electronic Hamiltonian and asserted that the wave function of
N electrons must be antisymmetric under the exchange of any two electrons. Chapter 2 takes that
single requirement and, with almost nothing else, constructs the entire machinery that will carry us
through Hartree–Fock, configuration interaction, perturbation theory, and coupled cluster.
These notes follow the chapter section by section, keep the book’s notation, and fill in every step of
the derivations that Szabó & Ostlund either sketch or leave as an exercise. In particular we derive
the Slater–Condon rules in detail, develop second quantization from scratch, and prove the key
operator identities that reappear constantly later.

Notation. Lower-case i, j, k, l, . . . label occupied spin orbitals; a, b, c, d, . . . label virtual (unoccu-

pied) spin orbitals; p, q, r, s, . . . label generic spin orbitals. A spin orbital χ(x) is a function of the
combined space–spin coordinate x = (r, ω). Spatial orbitals are denoted ψ(r) and spin functions
α(ω), β(ω).

1 The electronic problem

After the Born–Oppenheimer separation, the electronic Schrödinger equation for N electrons in the
field of M fixed nuclei is
Helec Φ(x1 , . . . , xN ) = Eelec Φ(x1 , . . . , xN ), (1)
with the electronic Hamiltonian (atomic units)
X X X ZA X 1
Helec = − 21 ∇2i − + . (2)
riA rij
i i A i<j

The three pieces are the electronic kinetic energy, the electron–nucleus attraction, and the electron–
electron repulsion. Adding the fixed nuclear–nuclear repulsion gives the total energy
X ZA ZB
Etot = Eelec + .
RAB
A<B

The crucial property of Φ is not that it solves the Schrödinger equation — for interesting N that is
impossible analytically — but that it must be antisymmetric under exchange of any two electrons.
Everything in this chapter is a consequence of enforcing antisymmetry in a computationally usable
way.

1
 Szabó & Ostlund · Chapter 2 Notes

2 Orbitals, spin orbitals, spatial orbitals

A spatial orbital ψ(r) is a one-electron function of position. The set {ψi (r)} is normally chosen
orthonormal, Z
ψi∗ (r) ψj (r) dr = δij . (3)

An electron has spin as well as position, so a complete one-electron function must include a spin
coordinate ω taking two values. The two orthonormal one-electron spin functions are α(ω) and
β(ω), with
⟨α | α⟩ = ⟨β | β⟩ = 1, ⟨α | β⟩ = ⟨β | α⟩ = 0. (4)
A spin orbital χ(x) is the product of a spatial orbital and a spin function,
χ(x) = ψ(r) α(ω) or χ(x) = ψ(r) β(ω). (5)
From K spatial orbitals we can build 2K spin orbitals, orthonormal as
Z
χ∗i (x) χj (x) dx ≡ ⟨χi | χj ⟩ = δij . (6)

The use of spin orbitals is a huge convenience: formulas look like those of spinless one-particle
quantum mechanics but with spin silently included.

3 The Hartree product and why it fails

If electrons were distinguishable, independent particles, the N -electron wave function would be a
simple product of one-electron spin orbitals — a Hartree product:
ΦHP (x1 , . . . , xN ) = χi (x1 ) χj (x2 ) · · · χk (xN ). (7)
It satisfies the separable equation
X 
ĥ(i) ΦHP = (εi + εj + · · · + εk )ΦHP , (8)
i

with ĥ(i) a one-electron Hamiltonian and εi the eigenvalue of χi . Two things are wrong with this.
First, it is not antisymmetric under exchange of x1 ↔ x2 . Second, it pretends that electron 1 is in
χi , electron 2 in χj , . . . — it distinguishes the electrons. Electrons are indistinguishable fermions;
we must antisymmetrize.

4 Slater determinants
The simplest antisymmetric function built from N spin orbitals is the determinant introduced by
Slater,
χi (x1 ) χj (x1 ) · · · χk (x1 )
1 χi (x2 ) χj (x2 ) · · · χk (x2 )
Ψ(x1 , . . . , xN ) = √ .. .. .. .. . (9)
N! . . . .
χi (xN ) χj (xN ) · · · χk (xN )
Each row is labelled by an electron, each column by a spin orbital. Two key properties follow from
the algebraic properties of the determinant.

Page 2
 Szabó & Ostlund · Chapter 2 Notes

ˆ Antisymmetry. Interchanging two electrons interchanges two rows, multiplying the determinant
by −1.
ˆ Pauli exclusion. If two spin orbitals are identical, two columns coincide and Ψ = 0: no two
electrons can occupy the same spin orbital.

The prefactor (N !)−1/2 normalizes Ψ to unity: the determinant expands as N ! signed products, and
when we compute ⟨Ψ|Ψ⟩ we get N ! orthonormal pieces (cross terms vanish by orthonormality of the
χ’s), so the prefactor squared cancels the N !.

4.1 Compact notation

Writing the full determinant is cumbersome, so we abbreviate

Ψ = |χi χj · · · χk ⟩ , (10)

where the (N !)−1/2 , the antisymmetry, and the electron labels are implicit. Swapping any two spin
orbitals in the list changes the sign:

|χi χj χk · · ·⟩ = − |χj χi χk · · ·⟩ . (11)

4.2 The antisymmetrizer

A useful abstraction is the antisymmetrizer Â, defined as

1 X
 = (−1)p P̂ , (12)
N!
P

where the sum runs over all N ! permutations P̂ of electron labels and p is the parity of the
permutation (even = 0, odd = 1). Â has three properties we will use constantly:

ˆ Idempotent: Â2 = Â. Applying antisymmetrization twice is the same as once.

ˆ Hermitian: † = Â, because P̂ −1 has the same parity as P̂ .
ˆ Commutes with Ĥ: [Â, Ĥ] = 0, since Ĥ is symmetric under electron permutations.

In this language a Slater determinant is

√  
Ψ = N ! Â χi (x1 )χj (x2 ) · · · χk (xN ) , (13)

that is, the antisymmetrizer acting on a Hartree product, rescaled so that ⟨Ψ|Ψ⟩ = 1.

5 Form of the exact wave function: configuration interaction

A single Slater determinant is rarely the exact ground state. What is true is far more powerful: the
set of all Slater determinants that can be built from a complete one-electron basis is a complete
basis for N -electron antisymmetric functions. The exact wave function may be expanded as a linear
combination of determinants — configuration interaction (CI).

Page 3
 Szabó & Ostlund · Chapter 2 Notes

With 2K spin orbitals and N occupied to form a reference |Ψ0 ⟩, we label determinants that differ
from the reference by their excitation level:
E E
|Ψai ⟩ (single), Ψabij (double), Ψabc
ijk (triple), . . .

The exact wave function is

X 1 X ab ab E 1 X abc abc E
|Φ0 ⟩ = c0 |Ψ0 ⟩ + cai |Ψai ⟩ + cij Ψij + cijk Ψijk + · · · (14)
4 36
ia ijab ijkabc

The combinatorial factors (1/4, 1/36, . . . ) prevent double counting since the sums run independently.
Truncations define the approximations CIS, CISD, CISDT, . . . ; the untruncated sum is full CI,
which is exact within the given one-electron basis.

6 Matrix elements between Slater determinants: the Slater–Condon

rules

All of quantum chemistry rests on knowing how to compute ⟨Ψ|Ô|Ψ′ ⟩ for determinants Ψ, Ψ′ and
symmetric one- and two-electron Ô. The Slater–Condon rules are the technical core of Chapter 2.
Write the electronic Hamiltonian as
X X X ZA 1
Ĥ = ĥ(i) + v̂(i, j), ĥ(i) = − 12 ∇2i − , v̂(i, j) = . (15)
riA rij
i i<j A

Rules depend on how many spin orbitals differ between Ψ and Ψ′ : 0, 1, 2, or ≥ 3. Let Ψ = |χ1 · · · χN ⟩
be normalized with its spin orbitals in canonical order.

6.1 Working identity

√
Because Ψ = N ! Â[χ1 (1) · · · χN (N )] and  is Hermitian, idempotent, and commutes with any
symmetric Ô,
X
⟨Ψ|Ô|Ψ⟩ = N ! ⟨χ1 (1) · · · χN (N )|Ô Â|χ1 (1) · · · χN (N )⟩ = (−1)p ⟨χ1 (1) · · ·|Ô P̂ |χ1 (1) · · ·⟩ . (16)
P
√
The 1/N ! from  cancels the ( N !)2 from normalisation. This identity — the matrix element of
Ô between antisymmetric functions equals the signed sum of matrix elements against the Hartree
product and its permutations — is the workhorse below.

6.2 Case 1: diagonal matrix elements (Ψ = Ψ′ )

P
⟨Ψ|Ψ⟩ = 1. For the one-electron operator Ô1 = i ĥ(i): only the identity permutation survives in
(16) (any non-identity permutation moves at least two labels; a one-electron operator leaves N − 1
labels alone, and at least one must then mismatch by orthonormality). Hence
X X X
⟨Ψ|Ô1 |Ψ⟩ = ⟨χi |ĥ|χi ⟩ ≡ ⟨i|ĥ|i⟩ ≡ hii . (17)
i i i

Page 4
 Szabó & Ostlund · Chapter 2 Notes

P
For the two-electron operator Ô2 = i<j v̂(i, j) two permutations survive: the identity (Coulomb)
and the transposition (i j) (exchange, with sign −1 from its odd parity). The result is
X X
⟨Ψ|Ô2 |Ψ⟩ = 12 ⟨ij | ij⟩ − ⟨ij | ji⟩ = 12

⟨ij ∥ ij⟩ , (18)
ij ij

where the physicist’s two-electron integrals and the antisymmetrized integral are
ZZ
1
⟨pq | rs⟩ ≡ χ∗p (x1 )χ∗q (x2 ) χr (x1 )χs (x2 ) dx1 dx2 , ⟨pq ∥ rs⟩ ≡ ⟨pq | rs⟩ − ⟨pq | sr⟩. (19)
r12
Thus the total diagonal energy of a Slater determinant is
X X
1
⟨Ψ|Ĥ|Ψ⟩ = ⟨i|ĥ|i⟩ + 2 ⟨ij ∥ ij⟩ . (20)
i ij

This is the starting point of Chapter 3.

6.3 Case 2: one spin orbital different

Arrange the determinants in maximum coincidence. Suppose Ψ has χa where Ψ′ has χb ; the other
N − 1 spin orbitals match. Then

Ψ i ĥ(i) Ψ′ = ⟨a|ĥ|b⟩ ,
P
(21)
X
Ψ i<j v̂(i, j) Ψ′ =
P
⟨ac ∥ bc⟩ , (22)
c

with c running over the N − 1 common spin orbitals. For the one-electron piece, only the identity
permutation survives, and the non-matching factors pick out ⟨a|ĥ|b⟩. For the two-electron piece,
the Coulomb pairing (identity) and exchange pairing (transposition of the distinguished electron
with each common c) combine into the antisymmetrized integral. Thus
X
Ψ Ĥ Ψ′ = ⟨a|ĥ|b⟩ + ⟨ac ∥ bc⟩ . (23)
c

6.4 Case 3: two spin orbitals different

Now Ψ has (χa , χb ) where Ψ′ has (χc , χd ), all else identical. A one-electron operator cannot bridge a
two-orbital difference, so its matrix element is zero. Two permutations survive for the two-electron
operator — identity and transposition of the two distinguished electrons — giving

Ψ Ĥ Ψ′ = ⟨ab ∥ cd⟩ . (24)

6.5 Case 4: three or more spin orbitals different

A one-electron operator can change at most one label in a non-vanishing matrix element; a two-
electron operator at most two. Therefore

Ψ Ĥ Ψ′ = 0 if Ψ and Ψ′ differ in three or more spin orbitals. (25)

Page 5
 Szabó & Ostlund · Chapter 2 Notes

6.6 Summary of Slater–Condon rules

ˆ 0 differences: ⟨Ψ|Ĥ|Ψ⟩ = 1
P P
i hii⟨ij ∥ ij⟩.
+ 2 ij

ˆ 1 difference (χa ↔ χb ): ⟨Ψ|Ĥ|Ψ′ ⟩ = ⟨a|ĥ|b⟩ + c ⟨ac ∥ bc⟩.

P

ˆ 2 differences (χa χb ↔ χc χd ): ⟨Ψ|Ĥ|Ψ′ ⟩ = ⟨ab ∥ cd⟩.

ˆ ≥ 3 differences: ⟨Ψ|Ĥ|Ψ′ ⟩ = 0.

Phase warning. These formulas assume the two determinants are in maximum coincidence with
their differing spin orbitals in the same column position. Otherwise a sign (−1)p appears, where p
is the number of transpositions needed to bring them to coincidence.

7 Coulomb and exchange integrals; integrating out the spin

The operator 1/r12 is spin-independent, so spin integrations can be done first, leaving spatial
integrals. Let χi (x) = ψa (r) σ(ω) with σ ∈ {α, β}. Then
ZZ
1
⟨ij | kl⟩ = ψa∗ (r1 )σi∗ (ω1 ) ψb∗ (r2 )σj∗ (ω2 ) ψc (r1 )σk (ω1 ) ψd (r2 )σl (ω2 ) dx1 dx2 = δσi σk δσj σl [ab|cd],
r12
(26)
where the chemists’ (Mulliken) spatial two-electron integrals are
ZZ
1 ∗
[ab|cd] ≡ ψa∗ (r1 )ψc (r1 ) ψ (r2 )ψd (r2 ) dr1 dr2 . (27)
r12 b
Physicists’ notation groups by electron: first two indices on electron 1, last two on electron 2.
Chemists’ notation groups by electron pair. Convert using ⟨ij | kl⟩ = [ik|jl].
Because of the Kronecker deltas, the Coulomb integral ⟨ij | ij⟩ = [ii|jj] is nonzero for any spins,
while the exchange integral ⟨ij | ji⟩ = [ij|ji] requires the spins of i and j to match. In closed shells,
this makes parallel-spin electrons repel less on average than antiparallel-spin ones — the origin of
Hund’s rule and of much of chemistry.

8 The Coulomb and exchange operators

Diagonal matrix elements admit an equivalent operator form that is used constantly. Define two
one-electron operators acting on a test function χ(x1 ):
Z 
ˆ ∗ 1
Jb (1) χ(1) = χb (2) χb (2) dx2 χ(1), (28)
r12
Z 
1
K̂b (1) χ(1) = χ∗b (2) χ(2) dx2 χb (1). (29)
r12

Jˆb is the Coulomb operator : it multiplies χ by the classical potential of |χb |2 . K̂b is the exchange
operator : nonlocal, mixing “in” and “out” coordinates, with no classical analogue — purely a

Page 6
 Szabó & Ostlund · Chapter 2 Notes

consequence of antisymmetry. Then

⟨a|Jˆb |a⟩ = ⟨ab | ab⟩, ⟨a|K̂b |a⟩ = ⟨ab | ba⟩, (30)

and the diagonal HF energy takes the compact form

X X
E= ⟨i|ĥ|i⟩ + 12 ⟨i|Jˆj − K̂j |i⟩ . (31)
i ij

(Jˆj − K̂j ) is what electron i “sees” when electron j is in χj ; summing over j gives the mean field in
which electron i moves in Hartree–Fock theory.

9 Restricted and unrestricted determinants; closed-shell energy

A restricted closed-shell wave function assigns each occupied spatial orbital ψa both an α and a β
electron. For N = 2n,
|Ψ0 ⟩ = |ψ1 α ψ1 β ψ2 α ψ2 β · · · ψn α ψn β⟩ . (32)
Plugging this into the diagonal-rule formula and doing the spin integrations gives
X X

E=2 haa + 2Jab − Kab , (33)
a ab

with haa = ⟨a|ĥ|a⟩, Jab = [aa|bb], Kab = [ab|ba] over spatial orbitals. The factor of 2 in 2Jab comes
from the four spin combinations (αα, αβ, βα, ββ) contributing to Coulomb, whereas only like-spin
pairs contribute to exchange.
An unrestricted Hartree–Fock (UHF) wave function allows different spatial orbitals for α and β
electrons. UHF handles open-shell and bond-breaking cases that RHF cannot, at the cost of not
being an eigenfunction of Ŝ 2 (spin contamination). The RHF/UHF distinction recurs throughout
the book.

10 Second quantization: the algebra of creation and annihilation

Second quantization reformulates many-electron quantum mechanics so antisymmetry is automatic.
We work with occupation-number vectors and operators that create or destroy electrons in specified
spin orbitals. The payoff: matrix elements follow from commutation relations alone, with no messy
permutation arguments.

10.1 Creation and annihilation operators

For each spin orbital χp , define a†p (create) and ap (annihilate) by

a†p |χq χr · · ·⟩ = |χp χq χr · · ·⟩ , (34)

ap |χp χq χr · · ·⟩ = |χq χr · · ·⟩ . (35)

If one tries to create an electron in an already-occupied orbital, the result is zero (duplicated column).
If one tries to annihilate an electron in an unoccupied orbital, the result is also zero. The vacuum
| ⟩ contains no electrons and satisfies ap | ⟩ = 0 for all p.

Page 7
 Szabó & Ostlund · Chapter 2 Notes

10.2 Anticommutation relations

Because determinants are antisymmetric, swapping two creations introduces a sign:

a†p a†q | ⟩ = |χp χq ⟩ = − |χq χp ⟩ = −a†q a†p | ⟩ . (36)

Hence (with the Hermitian conjugate)

{a†p , a†q } = 0, {ap , aq } = 0. (37)

A more subtle calculation gives the mixed anticommutator,

{ap , a†q } ≡ ap a†q + a†q ap = δpq . (38)

These three identities are the complete algebra. Every property of determinants follows from them.

10.2.1 Derivation of {ap , a†p } = 1

Act on a determinant |K⟩ in which χp is either occupied or not.

ˆ Case 1: χp occupied in K. Then ap |K⟩ = (−1)Np |K \ χp ⟩ (where Np counts the number of

spin orbitals preceding χp ), and a†p ap |K⟩ = (−1)Np (−1)Np |K⟩ = |K⟩. The other order gives
 

a†p |K⟩ = 0 since χp is already present. Thus (ap a†p + a†p ap ) |K⟩ = |K⟩.

ˆ Case 2: χp unoccupied in K. Then ap |K⟩ = 0, and a†p |K⟩ = (−1)Np |K ∪ χp ⟩, so ap a†p |K⟩ =
|K⟩. Sum again |K⟩.

For p ̸= q one ordering always annihilates first, and cancellations yield zero.

10.3 Number operator

n̂p = a†p ap counts whether χp is occupied:

n̂p |K⟩ = |K⟩ if χp ∈ K, n̂p |K⟩ = 0 otherwise. (39)

P
The total number operator N̂ = p n̂p satisfies N̂ |K⟩ = N |K⟩ for any N -electron determinant.

10.4 One- and two-electron operators

Any spin-free one-electron operator has the second-quantized form

X
Ô1 = ⟨p|ĥ|q⟩ a†p aq , (40)
pq

and a symmetric two-electron operator

1X
Ô2 = ⟨pq ∥ rs⟩ a†p a†q as ar . (41)
4 pqrs

Page 8
 Szabó & Ostlund · Chapter 2 Notes

The order of annihilation operators (as ar , not ar as ) ensures the antisymmetrized integral ⟨pq ∥ rs⟩
appears. The electronic Hamiltonian is therefore
X X
Ĥ = ⟨p|ĥ|q⟩ a†p aq + 1
4 ⟨pq ∥ rs⟩ a†p a†q as ar . (42)
pq pqrs

This is the form used in the rest of the book. It makes no reference to a particular determinant — it
acts on Fock space — and its matrix elements are computed by pushing anticommutators around.

10.5 Example: rederiving a Slater–Condon rule

Rederive Case 1 (diagonal one-electron matrix element). We want

X
⟨Ψ| ⟨p|ĥ|q⟩ a†p aq |Ψ⟩ .
pq

Since aq |Ψ⟩ = 0 unless q is occupied, and a†p aq |Ψ⟩ rebuilds |Ψ⟩ only when p = q, we have

⟨Ψ|a†p aq |Ψ⟩ = δpq np , (43)

with np = 1 if χp is occupied and 0 otherwise. Hence

X X
⟨Ψ|Ô1 |Ψ⟩ = np ⟨p|ĥ|p⟩ = ⟨i|ĥ|i⟩ , (44)
p i∈occ

exactly Case 1. Other Slater–Condon rules follow in the same manner: once anticommutators are
in hand, everything else is algebra.

10.6 Particle–hole formalism

For perturbation theory and coupled cluster it is convenient to measure excitations from a reference
|Ψ0 ⟩. We redefine the vacuum to be |Ψ0 ⟩ itself — the Fermi vacuum — and introduce particle/hole
operators:

ˆ For i occupied in |Ψ0 ⟩: b̂†i = ai (destroying an occupied electron = creating a hole).

ˆ For a virtual in |Ψ0 ⟩: b̂†a = a†a (creating a virtual = creating a particle).

E
A single excitation is |Ψai ⟩ = a†a ai |Ψ0 ⟩, a double excitation is Ψab
ij = a†a a†b aj ai |Ψ0 ⟩, and so on.
This is the natural language of post-HF methods in Chapters 4–6.

11 Spin operators: singlets, triplets, and Ŝ 2

The spin-free, nonrelativistic Hamiltonian commutes with Ŝz and Ŝ 2 , so eigenfunctions of Ĥ are
also eigenfunctions of total spin. Slater determinants are always eigenfunctions of Ŝz , but not in
general of Ŝ 2 .

Ŝz |Ψ⟩ = 12 (nα − nβ ) |Ψ⟩ , (45)

Page 9
 Szabó & Ostlund · Chapter 2 Notes

where nα , nβ are the numbers of α- and β-spin orbitals occupied. Ŝ 2 = Ŝz2 + 12 (Ŝ+ Ŝ− + Ŝ− Ŝ+ )
mixes determinants whose α/β content differs by a spin flip. A closed-shell RHF determinant is
automatically an Ŝ 2 eigenfunction with S = 0 (singlet).
For open-shell systems one forms spin-adapted configuration state functions (CSFs) — linear
combinations that are simultaneous eigenfunctions of Ŝz and Ŝ 2 . The two-electron triplet with
MS = 0,
1  
|T0 ⟩ = √ |ψ1 α ψ2 β⟩ + |ψ1 β ψ2 α⟩ , (46)
2
is a sum of two determinants and cannot be written as a single one.

12 Symmetry, Brillouin’s theorem, and outlook

12.1 Brillouin’s theorem

If |Ψ0 ⟩ is the Hartree–Fock determinant (spin orbitals chosen to make ⟨Ψ0 |Ĥ|Ψ0 ⟩ stationary against
orbital rotations), then the matrix element to any singly excited determinant vanishes:

⟨Ψ0 |Ĥ|Ψai ⟩ = 0 for all i, a. (47)

P
From the one-orbital-different rule, this matrix element equals ⟨i|ĥ|a⟩ + j ⟨ij ∥ aj⟩, which is exactly
fia , the off-diagonal element of the Fock operator. The HF stationarity condition imposes fia = 0
for i ∈ occ, a ∈ virt. This is why the lowest-order correction to HF comes from double excitations,
not singles: singles have no first-order coupling to the reference.

12.2 Spatial symmetry

When the molecule has a non-trivial point group, every molecular orbital carries a label (irreducible
representation). Matrix elements ⟨p|ĥ|q⟩ and ⟨pq ∥ rs⟩ vanish unless the direct product of the irreps
contains the totally symmetric representation. This blocks the Fock matrix, shrinks CI matrices,
and makes many computations practical.

12.3 What’s next

With Slater determinants, Slater–Condon rules, and second quantization in hand:

ˆ Chapter 3: Hartree–Fock approximation — determine spin orbitals variationally within the

single-determinant ansatz, producing the Fock operator and its SCF solution.
ˆ Chapter 4: Configuration interaction — expand beyond the reference, diagonalize the Hamilto-
nian matrix constructed with the Slater–Condon rules.
ˆ Chapter 5: Pair and coupled-pair theories — exponential ansätze in second-quantized language
to efficiently capture dominant correlation.

Each method is a particular strategy for choosing and weighting Slater determinants; the machinery
that makes them computable is precisely that of Chapter 2.

Page 10
 Szabó & Ostlund · Chapter 2 Notes

Key results at a glance

ˆ Slater determinant. Minimal antisymmetric N -electron wave function: Ψ =

(N !)−1/2 det[χi (xj )].
ˆ Antisymmetrizer. Â = 1 p
P
N! P (−1) P̂ ;
Hermitian, idempotent, commutes with Ĥ.

ˆ Hartree–Fock energy. ⟨Ψ|Ĥ|Ψ⟩ = i hii + 21 ij ⟨ij ∥ ij⟩.

P P

ˆ Slater–Condon rules. Matrix elements of Ĥ depend only on how many spin orbitals
differ (0,1,2); zero for 3 or more.

ˆ Second quantization. {ap , a†q } = δpq , {ap , aq } = {a†p , a†q } = 0; Ĥ = †

P
pq hpq ap aq +
1P † †
4 pqrs ⟨pq ∥ rs⟩ ap aq as ar .

ˆ Jˆ vs K̂. Jˆb local (classical Coulomb); K̂b nonlocal, purely from antisymmetry.
ˆ Brillouin. For HF orbitals, ⟨Ψ0 |Ĥ|Ψai ⟩ = 0: singles decoupled at first order.
ˆ Spin. Determinants are always Ŝz eigenfunctions, not always Ŝ 2 eigenfunctions; spin
adaptation forms CSFs.

Suggested exercises on Chapter 2

1. Verify the normalisation factor (N !)−1/2 by computing ⟨Ψ|Ψ⟩ explicitly for N = 2 and N = 3.
2. Show that Â2 =  and † =  using  = N1 ! P (−1)p P̂ .
P

3. Derive the one-orbital-different Slater–Condon rule from the working identity (16). Identify
which permutations survive and why.
4. For a closed-shell two-electron system |ψ1 α ψ1 β⟩, do the spin integrations explicitly and reproduce
E = 2h11 + [11|11].

5. Verify {ap , a†q } = δpq on a simple two-orbital Fock space (basis kets | ⟩ , |1⟩ , |2⟩ , |12⟩).
6. Prove Brillouin’s theorem by writing ⟨Ψ0 |Ĥ|Ψai ⟩ via the one-orbital-different rule and identifying
the result with fia .
7. Construct the three triplet spin functions for a two-electron open-shell system (ψ1 ψ2 , ψ1 ̸= ψ2 )
and show each is an Ŝ 2 eigenfunction with S(S + 1) = 2.

Once you can do these seven problems fluently, you have mastered Chapter 2 — and with it the
technical foundation for the rest of the book.

Page 11