Erin Dahlke
Department of Chemistry
University of Minnesota
VLab Tutorial
May 25, 2006
Elementary Quantum Mechanics
HΨ = EΨ
H =T +V
N h2 2 M h2 2
N M Z e N N e2
α
M M Zα Z β
H =−∑ ∇i − ∑ ∇α − ∑ ∑ +∑ ∑ + ∑ ∑
i=1 2m e α =1 2Mα r
i=1α =1 iα i=1 j<i ij α =1 β >α rαβ
r
where the first two terms represent the kinetic energy of the electrons and
nuclei, respectively, the third term is the nuclear-electron attraction, the
fourth term is the electron-electron repulsion, and the fifth term is the
nuclear-nuclear repulsion.
Elementary Quantum Mechanics
Atomic units:
h =1 e =1
Mα
me = 1 MA =
me
N 1 2 M 1 N M Z N N 1 M M Z Z
2
H = − ∑ ∇i − ∑ ∇A − ∑ ∑ A +∑ ∑ + ∑ ∑ A B
i=1 2 A=1 2M A i=1 A=1 riA i=1 j<i rij A=1 B> A rAB
To a good approximation one can assume that the electrons move in a field
of fixed nuclei
N 1 2 N M ZA N N 1
Helec = − ∑ ∇ i − ∑ ∑ +∑ ∑
i=1 2 r
i=1 A=1 1A i=1 i=1 rij
M M Z A ZB
E tot = E elec + ∑ ∑
A=1 B> A rAB
What is a Wave Function?
For every system there is a mathematical function of the coordinates of the
system ⇒ the wave function (Ψ)
2
Ψ = Ψ* Ψ units of probability density
∫ i Ψi dτ = 1
Ψ *
∫ i Ψ j dτ = Sij
Ψ *
α= spin up
β = spin down
⎧ψ (r)α (ω )
⎪
χ (x) = ⎨ or
⎪ψ (r)β (ω )
⎩
Hartree Products
Consider a system of N electrons
N 1 N M Z N N 1
2
Helec = − ∑ ∇ i − ∑ ∑ A +∑ ∑
i=1 2 i=1 A=1 r1A i=1 i=1 rij
N
H = ∑ h(i)
i=1
Hartree Products
N
H = ∑ h(i)
i=1
Because the Hamiltonian is separable the wave function for this system
can be written as a product of the one-electron wave functions.
HΨHP = EΨHP
in which the total energy is simply a sum of the one-electron orbital
energies
E = εi + ε j + L + εk
Hartree Method
Instead of completely ignoring the
M Z
2
h(i) = − 2 ∇ i − ∑ k + Vi { j}
1 electron-electron interactions we
k=1 rik consider each electron to be moving in a
field created by all the other electrons
From variation calculus you can show that:
ρj
Vi { j} = ∑ ∫ r dr
j≠i ij
where 2
ρ j = Ψ*j Ψ j = Ψ j
2 2
Ψi Ψ j
E = ∑ εi − ∑ ∫ ∫
1
2
dri dr j
i i≠ j rij
2 2 2
χ i (x1 ) dx1 χ j (x 2 ) dx 2 L χ k (x N ) dx N
HP
Ψ12 (x1,x 2 ) = χ i (x1 ) χ j (x 2 )
HP
Ψ21 (x1,x 2 ) = χ i (x 2 ) χ j (x1 )
Slater Determinant
2
∫ ∫ ∫ ∫ Ψs dr1dr2 dω1dω 2 =
2
∫∫∫∫ 1 (1s(r )α (ω )1s(r )β (ω ) −1s(r )β (ω )1s(r )α (ω )) dr1dr2 dω1dω 2
2 1 1 2 2 1 1 2 2
2
Ψ = Ψ* Ψ
Slater Determinants
2
∫ ∫ ∫ ∫ Ψs dr1dr2 dω1dω 2 =
1[∫
2
∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ β * (ω 2 )β (ω 2 )dω 2
- ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )β (ω1 )dω1 ∫ β * (ω 2 )α (ω 2 )dω 2
- ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ β * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )β (ω 2 )dω 2
+ ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ β * (ω1 )β (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
2
∫ ∫ ∫ ∫ Ψs dr1dr2 dω1dω 2 =
1[∫
2
∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ β * (ω 2 )β (ω 2 )dω 2
- ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )β (ω1 )dω1 ∫ β * (ω 2 )α (ω 2 )dω 2
- ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ β * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )β (ω 2 )dω 2
+ ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ β * (ω1 )β (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
∫ α * (ω )α (ω )dω = ∫ β * (ω )β (ω )dω = 1
∫ α * (ω )β (ω )dω = ∫ β * (ω )α (ω )dω = 0
Slater Determinants
2
∫ ∫ ∫ ∫ Ψs dr1dr2 dω1dω 2 =
1[∫
2
∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ β * (ω 2 )β (ω 2 )dω 2 1
- ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )β (ω1 )dω1 ∫ β * (ω 2 )α (ω 2 )dω 2 0
- ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ β * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )β (ω 2 )dω 2 0
+ ∫ ∫ 1s* (r1 )1s(r1 )1s* (r2 )1s(r2 )dr1dr2 ∫ β * (ω1 )β (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2 1
∫ α * (ω )α (ω )dω = ∫ β * (ω )β (ω )dω = 1
∫ α * (ω )β (ω )dω = ∫ β * (ω )α (ω )dω = 0
Slater Determinants
After integrating out the spin coordinates, we’re left with only
two terms in the integral:
2
∫ ∫ ∫ ∫ Ψs dr1dr2 dω1dω 2 =
1 [ ∫ 1s* (r )1s(r )dr ∫ 1s* (r )1s(r )dr + ∫ 1s* (r )1s(r )dr ∫ 1s* (r )1s(r )dr ]
2 1 1 1 2 2 2 1 1 1 2 2 2
2 2 2
∫ ∫ ∫ ∫ Ψs dr1dr2 dω1dω 2 = ∫ 1s(r1 ) dr1 ∫ 1s(r2 ) dr2
2 2
∫ ∫ ∫ ∫ Ψs* r1 Ψs dr1dr2 dω1dω 2 = ∫ ∫ 1s(r1 ) r1 ∫ 1s(r2 ) dr1dr2 = J ⇒ Coulomb repulsion
12 12
Coulomb Repulsion
Classically the Coulomb repulsion between two point charges is given by:
qq
J= 1 2
r12
He : 1s1 2s1
2
∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 =
1[∫
2
∫ 1s* (r1 )1s(r1 )2s* (r2 )2s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
- ∫ ∫ 1s* (r1 )2s(r1 )2s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
- ∫ ∫ 2s* (r1 )1s(r1 )1s* (r2 )2s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
+ ∫ ∫ 2s* (r1 )2s1s* (r2 )1s(r2 )(r1 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
Slater Determinants
2
∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 =
2
1 (1s(r )α (ω )2s(r )α (ω ) − 2s(r )α (ω )1s(r )α (ω )) dr1dr2 dω1dω 2
2 1 1 2 2 1 1 2 2
2
∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 =
1[∫
2
∫ 1s* (r1 )1s(r1 )2s* (r2 )2s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
- ∫ ∫ 1s* (r1 )2s(r1 )2s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
- ∫ ∫ 2s* (r1 )1s(r1 )1s* (r2 )2s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
+ ∫ ∫ 2s* (r1 )2s1s* (r2 )1s(r2 )(r1 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2
Slater Determinants
2
∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 =
2
1 (1s(r )α (ω )2s(r )α (ω ) − 2s(r )α (ω )1s(r )α (ω )) dr1dr2 dω1dω 2
2 1 1 2 2 1 1 2 2
2
∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 =
1[∫
2
∫ 1s* (r1 )1s(r1 )2s* (r2 )2s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2 1
- ∫ ∫ 1s* (r1 )2s(r1 )2s* (r2 )1s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2 1
- ∫ ∫ 2s* (r1 )1s(r1 )1s* (r2 )2s(r2 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2 1
+ ∫ ∫ 2s* (r1 )2s1s* (r2 )1s(r2 )(r1 )dr1dr2 ∫ α * (ω1 )α (ω1 )dω1 ∫ α * (ω 2 )α (ω 2 )dω 2 1
Slater Determinants
2
∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 =
1[∫
2
∫ 1s* (r1 )1s(r1 )2s* (r2 )2s(r2 )dr1dr2 − ∫ ∫ 1s* (r1 )2s(r1 )2s* (r2 )1s(r2 )dr1dr2
- ∫ ∫ 2s* (r1 )1s(r1)1s* (r2 )2s(r2 )dr1dr2 + ∫ ∫ 2s* (r1 )2s(r1 )1s* (r2 )1s(r2 )dr1dr2 ]
2 2 2
∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 ≠ ∫ 1s(r1) dr1 ∫ 1s(r2 ) dr2
∫ ∫ ∫ ∫ Ψt* r1 Ψt dr1dr2 dω1dω 2 = 12 (J − 2 ∫ 1s* (r1 )2s(r1 ) r1 1s(r2 )2s* (r2 )dr1dr2 + J)
12 12
exchange integral
=J −K
Exchange Integral
The exchange integral has no classical analog.
∫ 1s* (r1 )2 s(r1 ) r1 1s(r2 )2 s* (r2 ) dr1dr2 = ∫ 1s* (r1 )2 s* (r2 ) r1 1s(r2 )2 s(r1 ) dr1dr2
12 12
The exchange integral gets its name from the fact that the two electrons
exchange their positions as you go from the left to the right in the
integrand.
Electrons of like spin tend to avoid each other more than electrons of
different spin, so the destabilization predicted by the Coulomb integrals is
too high. The exchange integrals, which are always positive, lower the
overall repulsion of the electron (~25%).
Slater Determinants
2
∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 =
1 [ ∫ 1s* (r )1s(r )dr ∫ 2s* (r )2s(r )dr − ∫ 1s* (r )2s(r )dr ∫ 2s* (r )1s(r )dr ]
2 1 1 1 2 2 2 1 1 1 2 2 2
- ∫ 2s* (r1 )1s(r1 )dr1 ∫ 1s* (r2 )2s(r2 )dr2 + ∫ 2s* (r1 )2s(r1 )dr1 ∫ 1s* (r2 )1s(r2 )dr2 ]
2
when r1 = r2 ∫ ∫ ∫ ∫ Ψt dr1dr2 dω1dω 2 = 0
So no two electrons with the same spin can occupy the same point
in space ⇒ the Pauli Exclusion principle
Hartree–Fock Theory
What if we apply Hartree theory to a Slater determinant wave function?
nuclei Z
f (i) = − 12 ∇ i2 − ∑ k + V HF { j} one-electron Fock operator
i
k rik
Exchange operator:
• Since both J and K contain the self-interaction term, and since we’re
subtracting them from each other, the self-interaction cancels.
What is a Wave Function?
For every system there is a mathematical function of the coordinates of the
system ⇒ the wave function (Ψ)
2
Ψ = Ψ* Ψ units of probability density
∫ i Ψi dτ = 1
Ψ *
∫ i Ψ j dτ = Sij
Ψ *
b b
f (i)φi (x) = f (i) ∑ c yi χ y (x) = ∑ c yi f (i) χ y (x)
y=1 y=1
b b nuclei
Zk b
∑ c yi f (i) χ y (x) = ∑ c yi [− 12 ∇ i2 − ∑ + J(i) − K(i)]χ y (x) = εi ∑ c yi χ y (x)
y=1 y=1 k rik y=1
Hartree–Fock Theory
b b
J j (x1 ) = ∑ ∑ c *mj c nj ∫ χ *m (x 2 ) r1 χ n (x 2 )dx 2
12
m=1 n=1
b b
K j (x1 ) = ∑ ∑ c *mj c nj ∫ χ *m (x 2 ) r1 χ n (x1 )dx 2
12
m=1 n=1
b b b
∑ c yi Fzy −εi ∑ c yi Szy = 0 ∑ c yi (Fzy − εi Szy ) = 0
y=1 y=1 y=1
Where we will have one such equation for each electron is our system.
Hartree–Fock Theory
In order find a non-trivial solution to this set of equations one can set up
and solve the secular determinant:
E HF = ∑ εi − 12 ∑ J j (i) − K j (i)
i j
Choose a basis set Flow chart of the
implementation of
Choose a molecular geometry Hartree–Fock Theory
no
Is new density matrix P(n)
sufficiently similar to old
yes
Output data for given geometry density matrix P(n-1)
Limitations of Hartree–Fock Theory - Energetics
•Hartree–Fock theory ignores electron correlation
- cannot be used (accurately) in any process in which the
total number of paired electrons changes.
•Even if the total number of paired electrons stays the same, if the
nature of the bonds changes drastically HF theory can have serious
problems. (i.e., isomerization reactions)
•Will not do well for describing systems in which there are dispersion
interactions, as they are completely due to electron correlation effects,
except by cancellation of errors.
•Bad for transition state structures due to the large correlation associated
with the making and breaking of partial bonds.