CHEM 580

Computational Chemistry
Fall 2020
From Schrodinger to Hartree-
Fock
 COURSE OVERVIEW
• Objective: Learn to use quantum chemistry for your
research
• There will be some math
– No derivations
– No programming
• Text: Jensen: Intro to Computational Chemistry 3rd Ed
• Course grade
– Mid-term exam (take-home): 40%
– Research project (paper): 40%
– Class seminar on research project: 20%
• Choose project in consultation with major prof & me
– The sooner the better: always glitches
 COURSE OVERVIEW
• Timing
– Semester is 1 week shorter than normal
– Class time is 5 minutes shorter than normal = 1 week less
– Knowledge of point groups will be assumed
• Important for GAMESS (and other) input files
• Questions in class
– Stay muted during lecture
– Use chat function in zoom
– I will ask for questions regularly
 COURSE OVERVIEW
• About your research projects
– Last two weeks of class will be devoted to your talks
– Final paper on project will be due early in week of finals
• Paper should be organized as a journal publication
• Abstract, intro, methods, results, conclusions
• Relevant references
– Outline of project due no later than September 17
• Include your thoughts about the project in consultation with your
major professor if you have one
• Discuss with me if you have not chosen a major prof yet (or even if
you have)
• We can set up skype/zoom calls to discuss
 COURSE OVERVIEW
• Focus: Quantum chemistry/electronic structure theory
– GAMESS: General Atomic and Molecular Electronic
Structure System
– Available for download:
https://www.msg.chem.iastate.edu/gamess/download.html
– Can run on most computers including laptops
– Class project will need more capable computer
• Chemistry cluster: Crunch
• System Manager: Justin Conrad
– Other QC programs
• NWChem: Open source, free download
• Psi4: Open source, free download
• Most others cost real dollars
– Non-QC methods/programs: Molecular Mechanics (MM)
 From Schrödinger to Hartree-Fock
Objective: Solve the Schrödinger equation for
 •

chemistry problems
– Not possible except for H atom
– Solution: introduce approximations
– One-electron functions called “orbitals”
• Convenient mathematical constructs: not real
• J. Phys. Chem. A, 121, 4851 (2017)
• Schrödinger equation is an eigenvalue equation:
– (Operator) function = (constant) function
– Operator examples: d/dx; exp; •;
– Example eigenvalue equation: d/dx (eax)=a(eax)
– d/dx=operator, eax=eigenfunction, a=eigenvalue
 Schrödinger equation (SE)
Ĥ   E 

𝐻is the Hamiltonian operator.

 ^
 𝐸 is the energy of the system (eigenvalue)
𝛹
  is the wave function (eigenfunction) that contains all needed information about
the system
Square of the wave function = probability density: Heisenberg
Determines all properties
The Hamiltonian
The Hamiltonian in the SE has the following form for atoms:
N N M N N
Hˆ   Tˆi   VˆiA   Vˆij
i 1 i 1 A1 i 1 j i

Kinetic energy Potential Potential

operator of energy operator energy operator
electron i between proton between
A and electron I electrons i and j
attractive repulsive
 Atomic units (au)
The SE is generally solved in atomic units. Atomic units definition:

SI units Atomic units

Mass of the electron 9.109382*10-31 kg 1
(me)
Proton charge e 1.6021765*10-19 C 1
ћ 1
h 6.626069*10 34
4πε0  J s 1
2 2
4  8.8541878*1012 C 2 N 1m2 

me e 4
Energy unit: 1Hatree   27.21138eV  627.5095kcal / mol  2625.5kJ / mol
 4 0 
2 2

4 0  2
Length unit: 1Bohr   0.5291772Å
me e 2
 Example
What is the C-H distance in methane in Bohr? (d(C-H)=1.09Å)?
What is the bond dissociation energy? (E=105 kcal/mol)

1bohr
d (C  H )  1.09Å *  2.06bohr
0.5291772Å

1hartree
E (C  H )  105kcal / mol *  0.1673hartrees
627.5095kcal / mol
 The Roadblock
The Hamiltonian in the SE has the following form:
N N M N N
Hˆ   Tˆi   VˆiA   Vˆij
i 1 i 1 A1 i 1 j i

 Ti = -1/2 I2: 2 = d2/dx2 + d2/dy2 + d2/dz2

ViA = -ZA/riA: ZA=nuclear charge on atom A; riA = distance between nucleus A &
electron i

The SE cannot be solved exactly because of the Vij term = i/rij.

rij = distance between electron i and j =[(xi-xj)2 + (yi-yj)2 + (zi-zj)2]1/2

Not separable: Many-body problem

For what system can we solve the SE exactly?

 Hydrogen atom
Hˆ  Tˆ1  Vˆ1N
Just one electron: no Vij term
The wave function solution to the SE for the hydrogen atom defining the
orbitals is given by:

 n ,l ,m  r ,  ,    Rn,l  r  Yl m   ,  

Radial function Spherical harmonics

n=1,2,3… Principal quantum number

l=0,1,2…n-1 Angular quantum number
|m|≤l Magnetic quantum number
The radial function and spherical
harmonics

Note: a0 = 1 in atomic units

 Real hydrogen-like wave
functions (orbitals)
Spherical harmonics are complex. In order to work with real functions, we
take linear combinations of the complex spherical harmonics.

s orbital

p orbitals

d orbitals
 Hydrogen atom Energy levels
In SI units, The energy levels of the hydrogen atom are given by:

Z= Number of protons in the nucleus

µ= reduced mass (kg): memp/(me+mp)
 Z 2  e4 e= charge of the proton (C)
En 
8 0 n 2 h 2 n= principal quantum number
h= Plank’s constant (J.s)
ε0=permittivity (C2.N-1.m-2)
In atomic units, the energy levels of the hydrogen atom are given by:

Z 2
En  2
2n
Note: The energy depends on n only. Not on l and m. Therefore, states with the same n and
different l and m (i.e., 2s and 2p) are degenerate.
H atom ground state energy

Z2 1
En   2   hartree
2n 2

Units: 1 hartree = 27.21 eV = 627.517 kcal/mol)

En = -1/2 h = -13.6 eV = -313.76 kcal/mol
So, first ionization potential (IP) for H = 13.6 eV

How do we deal with heavier atoms?

Simplest is He.
 Helium atom
N N M N N
Hˆ   Tˆi   VˆiA   Vˆij
i 1 i 1 A1 i 1 j i

N = 2 (electrons) The SE equation cannot be solved exactly due to the electron repulsion [Vij =
1/rij] in the Hamiltonian. Many-body problem.
What can we do?

1) Ignore the electron repulsion (independent particle model)

Hˆ  Tˆ1  Vˆ1N  Tˆ2  Vˆ2 N  ¿ 𝑯 (𝟏 )+ 𝑯 ( 𝟐 ) =𝑯 (𝟎)

The Hamiltonian is the sum of two Hydrogen-like Hamiltonians that we

can solve exactly and separately:
 1 3/ 2  Zr1   1 3/2  Zr2 
Hˆ (1) (1)  E1 (1)    (1) (2)   Z e  Z e 
    
ˆ
H (2) (2)  E2 (2)
E  E1  E2
 He ground state energy in
independent particle model
2Z 2
EHe  E1  E2   2  4hartree = E(0)
2n
Experimental EHe = -2.905 Hartree

37.7 % error. 1.1 Hartree error = 687 kcal/mol error

cf. NN triple bond energy in N2 = 245 kcal/mol; De CO in CO = 258 kcal/mol

So, % error is not too meaningful: Absolute error > strongest bonds
Energy is too low/too negative: Due to ignoring electron repulsion.
Not stonks!
How do we fix this?
1. Perturbation theory
2. Variational principle
 Perturbation Theory
Use independent particle wave function (orbitals)
Use 1/r12 as a perturbation to correct the zeroth order Hamiltonian

Hˆ  Tˆ1  Vˆ1N  Tˆ2  Vˆ2 N  Vˆ12

Unperturbed Hamiltonian. We know the Small perturbation

exact solution to the SE: (E0=-4 hartree)

Using perturbation theory we can derive a correction to E(0) due to the

electron repulsion:
ˆ 5
E    V12  d  Z  2.75hartree = E(0) + E(1)
(0)  (0)

8
Error = 0.15 h = 94 kcal/mol: better
 Variational Principle
Expectation values (average values)
Observable energies are eigenvalues of the Hamiltonian.
We do not have eigenvalues for many-electron atoms due to the many-
body problem
So, the best we can do is find an energy that is an average over all
possibilities: expectation value: <E>
N

E i
Classically, we would say: E  i 1

In quantum mechanics: E     Hˆ d   Hˆ 

 Variational Principle
The expectation value can be expressed as:

E     Hˆ d   Hˆ 

Variation theorem: The expectation value of the energy for any

normalized trial wavefunction Ф is an upper bound to the true ground
state energy E0.
Etrial   Hˆ   E0
Effective atomic
Trial function for He: number
 1 3/2  r1 
   1s (1) 1s (2)  1s (1)    e  Variational
   parameter

 1 3/2  r2 
 1s (2)    e 
  
If z =Z = 2, we get the same result as perturbation theory: E = - 2.75 Hartree.
Find the value of z that gives us the lowest energy: Satisfies the variational
principle
 Apply Variational Principle

The value of z that minimizes the energy is 1.69 < Z=2.

Why?
The 1s orbital we are using was obtained for H atom with just one electron.
Now we are forcing 2 electrons into that same little orbital. Will they be
happy?
They will want to get away from each other: Larger orbital, less repulsion
The resulting minimized energy is -2.85 Hartree: Closer to the experimental
value of -2.9 hartree. Error is down to 0.05 Hartree = 30 kcal/mol
 Spin and Antisymmetry
 He   1s (1) 1s (2)
Indistinguishability: The wave function of a system of identical interacting
particles (e.g., electrons) must not distinguish among the particles.
Antisymmetry: The total wave function of a system of electrons must be
antisymmetric with respect to interchange of any two electrons. For
instance, for a two-electron system:

 (1, 2)   (2,1)
ΨHe satisfies indistinguishability, but not antisymmetry: It is symmetric
to exchange of electrons 1 & 2. What are we missing here?
Electron spin. Each electron has an intrinsic property called “spin”,
based on two quantum numbers: s=1/2; ms= ± ½

ms=+½: spin “up”, a spin; ms=-½: spin “down”, b spin

 Spin and Antisymmetry
Hydrogen atom has just one electron: could be either a or b. These two
possibilities are degenerate (same energy).
Antisymmetry is not an issue

    x, y, z  g  ms 
g (ms) = α(ms=1/2) or β(ms=-1/2)

He atom has 2 electrons, so the wave function must be antisymmetric.

The space function is symmetric.
 He  1s(1)1s(2)
The solution lies in the spin function. Possible spin functions for 2 electrons:

G1 = a(1)a(2)
G2 = b(1)b(2)
G3 = a(1)b(2)
G4 = a(2)b(1)
 Spin and Antisymmetry
Get proper antisymmetric wave function by multiplying the symmetric
space function by a spin function. But, which one? Need an
antisymmetric spin function to get an antisymmetric wave function.

G1 = a(1)(2)
a(2) symmetric
G2 = b(1)b(2) symmetric
G3 = a(1)b(2) neither symmetric nor antisymmetric. Not indistinguishable
G4 = a(2)(1)
b(1) neither symmetric nor antisymmetric. Not indistinguishable

Now what?
Take linear combinations of G3 and G4 to get one symmetric and one
antisymmetric spin function:
G5 = 2-1/2 [a(1)b(2) + a(2)b(1)] symmetric
G6 = 2-1/2 [a(1)b(2) - a(2)b(1)] antisymmetric

2-1/2 is a normalization factor

 Spin and Antisymmetry
Two possible wave functions that satisfy indistinguishability:

1
 [1s (1)1s (2)]  (1)  (2)   (2)  (1)  symmetric
2
1
 [1s (1)1s (2)]  (1)  (2)   (2)  (1)  antisymmetric:
2

The antisymmetric wave function is the correct ground state wave

function for He atom.
For more than two electrons, cannot simply multiply a space function
times a spin function: There are only two spin functions!
Need a better strategy
 Slater Determinants
The total orbital-based wave function for the ground state of Helium is:
1
 He  [1s(1)1s(2)]   (1)  (2)   (2)  (1) 
2
This wave function can also be written as a determinant, named for Slater:
1 1s (1) (1) 1s(1)  (1)   means 1sa; means 1sb
1s
 He   1s 1s
2 1s (2) (2) 1s (2)  (2) Spin orbitals

A Slater determinant is ALWAYS antisymmetric.

A general expression for the Slater determinant for many electrons is
 i  1  j  1 ... ...  k  1
i  2   j  2  ... ...  k  2 
1
       i  j ...  k
N!
    
i  N   i  N  ... ...  k  N 

ci are called spin orbitals, products of space and spin functions: c=ys [1sa]
 Example: Slater determinant
for Be atom
1s(1) 1s(1) 2 s(1) 2 s(1)
1 1s (2) 1s(2) 2 s(2) 2 s(2)
  1s 1s 2 s 2 s
24 1s(3) 1s(3) 2s (3) 2s(3)
1s (4) 1s(4) 2 s(4) 2 s(4)

NOTE: For a molecule we just replace the atomic orbitals 1s, 2s with
molecular orbitals. Stay tuned!
 Pauli Exclusion Principle
What happens if we put the two electrons in a 1s orbital and give them
both α spin?

1 1s (1) (1) 1s (1) (1)

 He   1s 1s
2 1s(2) (2) 1s (2) (2)

Two columns of the determinant are identical: Determinant = 0: Wave

function = 0
1
 [1s (1)1s(2)]   (1) (2)   (2) (1)   0
2

Pauli exclusion principle – antisymmetry principle!

For the same reason, the 3rd electron in Li cannot go into the 1s
orbital.
 He Excited States

Consider the excitation of one of the He 1s electrons into the 2s orbital

Considering only space functions, there are two possibilities:
 1  1s (1)2s(2)
 2  1s(2)2 s (1)

Are these acceptable wave functions?

NO

Electrons are not treated as indistinguishable.

Antisymmetry is not satisfied.

What is the solution?

 He Excited States
Take linear combinations of the space functions:
1
 1s 2 s   1s(1)2s(2)  1s(2)2s(1) 
2
Are these wave functions symmetric or antisymmetric?

1
 1s 2 s   1s(1)2s(2)  1s(2)2s(1)  Symmetric: y1: multiply by antisym spin function
2
1
 1s 2 s   1s(1)2s(2)  1s(2)2s(1) Antisymmetric: y2: multiply by sym spin function
2
 He Excited States
Recall the four spin functions for 2 electrons:

G1 = a(1)(2)
a(2) symmetric
G2 = b(1)b(2) symmetric
G5 = 2-1/2 [a(1)b(2) + a(2)b(1)] symmetric
G6 = 2-1/2 [a(1)b(2) - a(2)b(1)] antisymmetric
Acceptable wave functions:
(symmetric space function)•(antisymmetric spin function)
(antisymmetric space function)•(symmetric spin function)

Acceptable wave functions:

Y1= y1G6
Y2 = y2G1 Y3 = y2G2 Y4 = y2G5 Same space function: same energy
Y2, Y3, Y4 are degenerate: All have the same energy
One energy level, three degenerate states
 Multiplicity: 2S+1
We have 4 possible excited state wave functions for Helium:

Y1=y1G6: non-degenerate: S = 0: 2S+1 = 1 (singlet state): multiplicity=1

Y2 = y2G1 Y3 = y2G2 Y4 = y2G5 S = 1: 2S+1 =3 (triplet state):

multiplicity=3
Recall Hund’s rule: We expect the triplet state to be lower in energy:
S=1: Ms=1, 0, -1: Three states with the same energy

The wave functions Y1 and Y4 are linear combinations of two

determinants, not just one determinant.
One determinant is always antisymmteric, but one determinant is not
necessarily spin correct.
Sometimes linear combinations of determinants are needed to get a
spin correct wave function.
 Slater Determinants

Suppose we have a Slater determinant wave function

 i  1  j  1 ... ...  k  1
i  2   j  2  ... ...  k  2 
1
       i  j ...  k
N!
    
i  N   i  N  ... ...  k  N 

How do we apply the Variational Principle in the case of a general atom

or molecule?
How do we find those orbitals that are the best/optimal orbitals: those
orbitals that minimize the energy?
 Hartree-Fock theory
Consider a closed shell system (all electrons paired):

The wave function of this system can

be written as a Slater determinant:
Virtual (V) space ϕυ
  1  1 2  2 ... ...  N N

We want to find the orbitals that

minimize the total energy of the
system to satisfy the variational
Doubly occupied (D) ϕμ principle.
space
 Hartree-Fock theory
The total energy of the system is given by:

E  2 hii    2 J ij  K ij 
i i j

hii = 1 electron energy. Average kinetic energy and nuclear attraction energy.

Jii = Coulomb integral: Classical coulomb repulsion between electron clouds yi(r1)2 and
yj(r2)2

Kij = Exchange integral: Arises from the antisymmetry requirement.

The energy is invariant to any mixing of the D space orbitals among themselves
and any mixing of the V space orbitals among themselves.
So, how do we apply the variational principle to find those orbitals that
minimize the energy?
 Hartree-Fock theory
So, how do we apply the variational principle to find those orbitals that
minimize the energy?

Mix occupied with unoccupied orbitals! Find the optimal mixing

The minimization of the energy leads to the Hartree- ϕυ

Fock equations:
  
F i i i

  j (1)   (1)    (1)



h ii (1)  
j i
J 
 j (1)  K
j i
 i

i i ϕμ
 j (1) (1)   dr  * (2) 1  (2)   (1)
K i  2 j i  j
 r12 
Average field seen  
1
by the electron. J j (1)    dr2 *j (2)  j (2) 
 r12 

F = Fock operator; J = Coulomb operator; K = exchange operator

 Hartree-Fock theory

  
F i i i

Pseudo eigenvalue equation, because the Fock operator F depends on the orbitals.

HF equations must be solved iteratively:

Guess at the orbitals

Construct the Fock operator
Solve the HF equations for a new set of orbitals
Repeat until there is no change in the energy or orbitals for two iterations

Note the HF equations apply to both atoms and molecules.

The only difference is more nuclei, so more electron-nuclear attractions

 Koopman’s Theorem:
Ionization Potentials
Based on HF orbitals
Assumes frozen occupied orbitals upon electron removal
Then, the ionization potential (IP) is the negative of the
ϕυ orbital energy, –ε, of the orbital from which the electron is
removed.
εr
The electron affinity (EA) for adding an electron to a
εc virtual orbital is the negative of the energy of that virtual
orbital.

ϕμ IP   c
EA   r

Works best for main group elements

Not so great for transition metals
 Excited States
Again, assume frozen orbitals upon excitation from occupied orbital yi to
virtual orbital ya
Then, the excitation energy is given by:
1,3
Ei a   a   i  J ia  K ia  K ia
Jia is the Coulomb interaction between electrons in orbitals yi and ya

Kia is the corresponding exchange integral

The + is for the singlet state; the - is for the triplet state

εa

εi
 Unpaired Electrons: HF Open Shells
Two ways to treat open shell species:
Restricted open-shell (ROHF) or unrestricted (UHF)

ROHF UHF

Advantage: Spin correct Advantage: Takes full advantage

of variational principle. Different
Disadvantage: Does not take full orbitals for different spins.
advantage of the variational
principle Disadvantage: Not spin correct