Molecular Orbital Methods

a. Quantum mechanics background

b. Born-Oppenheimer approximation
c. The method (of solving Scrodinger equation)
d. Electron correlation
e. Basis sets

Whats it Good For?

Equilibrium and transition-state structures
Dipole and quadrapole moments and
polarizabilities
Vibrational frequencies, IR and Raman Spectra
NMR spectra
Electronic excitations and UV spectra
thermochemical data

Motivation
Schrdinger Equation can only be solved exactly for simple
systems.
Rigid Rotor, Harmonic Oscillator, Particle in a Box,
Hydrogen Atom
For more complex systems (i.e. many electron
atoms/molecules) we need to make some simplifying
assumptions/approximations and solve it numerically.
However, it is still possible to get very accurate results (and
also get very crummy results).
In general, the cost of the calculation increases with the
accuracy of the calculation and the size of the system.

Getting into the theory...

Three parts to solving the Schrdinger
equation for molecules:
Born-Oppenheimer Approximation
Leads to the idea of a potential energy surface
The expansion of the many-electron wave function in
terms of Slater determinants.
Often called the Method
Representation of Slater determinants by molecular
orbitals, which are linear combinations of atomic-likeorbital functions.
The basis set

The Born-Oppenheimer
Approximation

Time Independent Schrdinger Eq.

Well be solving the Time-Independent
Schrdinger Equation H
E
T
V

H
kinetic Epotential

Or:

Formanyelectronatoms/molecules:
2

h
H
2

1 2
h

2me
m

Nuclei
kinetic
energy

Electron
kinetic
energy

2
i

Z Z e2
r

Nuclear
Nuclear
repulsion

h2 d 2

2m dx 2

Z e
e


ri

i
j i j rij
Nuclear
electron
attraction

Electron
electron
repulsion

V
where:

2i

The Born-Oppenheimer
Approximation
The wave-function of the many-electron molecule is a
function of electron and nuclear coordinates: (R,r)
(R=nuclear coords, r=electron coords).
The motions of the electrons and nuclei are coupled.
However, the nuclei are much heavier than the electrons
mp 2000 me
And consequently nuclei move much more slowly than
do the electrons (E=1/2mv2). To the electrons the nuclei
appear fixed.
Born-Oppenheimer Approximation: to a high degree of
accuracy we can separate electron and nuclear motion:
(R,r)= el(r;R) N(R)

Electronic Schrdinger Equation

Now we can solve the electronic part of the Schrdinger
equation separately.
DiatomicPotentialEnergySurface(HgBr)
12

H (r; R) E (r; R)
2

h
H
el
2me

el

el

el

BO approximation leads
to the idea of a potential
energy surface.
U(R) E el VNN
Z Z e
VNN
r

Z e
e

i
i
j i j rij
2
i

U(R)

U(R)(kcal/mol)

el

Re

0
4

De
8
12
16
20

3.0

4.0

5.0

6.0

7.0

8.0

9.0

R(a0)
Atomicunitoflength
1bohr=1a0=0.529177

10.0

Nuclear Schrdinger Equation

Once we have the Potential Energy Surface (PES) we
can solve the nuclear Schrdinger equation.
(R) E (R)
H
N

2
h
1 2

H
U (R)
N
2
m

VibrationalEnergyLevelsofHF

50000

v=17
40000

U(R)(cm1)

Solution of the nuclear SE

allow us to determine a large
variety of molecular properties.
An example are vibrational
energy levels.

30000

20000

v=3
v=2
v=1
v=0

10000

1.0

1.5

2.0

2.5

3.0

R(a0)

3.5

4.0

4.5

5.0

The Method

So how do we solve Electronic

S.E.?
For systems involving more than 1 electron, still isnt
possible to solve it exactly.
2
2
2
h
Z
e

el
i
2me i
ri

i
j i j rij
The electron-electron interaction is the culprit

Approximating : The Method

After the B-O approximation, the next important
approximation is the expansion of in a basis of Slater
determinants:

el di i d0 0 d11 d2 2 ...
i

Slater Determinant:
1 (1) 1(1) 2 (1)K
1 1 (2) 1 (2) 2 (2)K
0
N! L
L
L
1 (N ) 1(N) 2 (N )K

M (1)
M (2)
L
M (N)

/ are spin-functions (spin-up/spin-down)

i are spatial functions (molecular orbitals
i and i are called spin-orbitals
Slater determinant gives proper anti-symmetry (Pauli
Principle)

Hartree-Fock Approximation
Think of Slater determinants as configurations.
Ex: Neon:
Ground-state electron configuration 1s22s22p6 this
would be 0
1 might be 1s22s22p53s1
If we had a complete set of is the expansion would be
exact (not feasible).
Hartree-Fock (HF) Approximation: Use 1 determinant, 0.
A variational method (energy for approximate will
always be higher than energy of the true )
Uses self-consistent field (SCF) procedure
Finds the optimal set of molecular orbitals for 0
Each electron only sees average repulsion of the
remaining electrons (no instantaneous interactions).

Accuracy of Hartree-Fock
Calculations

Hartree-Fock wavefunctions typically recover ~99% of the total

electronic energy.
total energy of O-atom -75.00 Eh (1 Hartree= 1 Eh = 2625.5
kJ/mol).
1 % of total energy is 0.7500 Eh or ~1969 kJ/mol
With more electrons this gets worse. Total energy of S atom
-472.88 Eh (1% of energy is 12415 kJ/mol)

Fortunately for the Hartree-Fock method (and all Quantum Chemists)

chemistry is primarily interested in energy differences, not total
energies. Hartree-Fock calculations usually provide at least qualitative
accuracy in this respect.
Bond lengths, bond angles, vibrational force constants,
thermochemistry, ... can generally be predicted qualitatively with
HF theory.

Electron correlation

Electron Correlation

Electron Correlation: Difference between energy calculated with exact

wave-function and energy from using Hartree-Fock wavefunction.
Ecorr = Eexact - EHF

Accounts for the neglect of instantaneous electron-electron

interactions of Hartree-Fock method.
In general, we get correlation energy by adding additional Slater
determinants to our expansion of .

el
0is often
HF
Hartree-Fock wavefunction
used i asi our starting point.
i 1
Additional Slater determinants are often called excited.
Mental picture of orbitals and electron configurations must be
abandoned.
Different correlation methods differ in how they choose which i to
include and in how they calculate the coefficients, di.

OrbitalEnergy

Excited Slater Determinants

HF

Stype

Stype

Dtype Dtype

Ttype

Qtype

Configuration Interaction
Write as a linear combination of Slater Determinants and calculate
the expansion coeficients such that the energy is minimized.

el d0 HF di i
i 1

Makes us of the linear variational principle: no matter what wave

function is used, the energy is always equal to or greater than the
true energy.
If we include all excited i we will have a full-CI, and an exact solution
for the given basis set we are using.
Full-CI calculations are generally not computationally feasible, so we
must truncate the number of i in some way.
CISD: Configuration interaction with single- and double-excitations.
Include all determinants of S- and D- type.
MRCI: Multireference configuration interaction
CI methods can be very accurate, but require long (and therefore
expensive) expansions.
hundreds of thousands, millions, or more

Mller-Plesset Perturbation
Theory

Perturbation methods, like Mller-Plesset (MP) perturbation theory,

assume that the problem wed like to solve (correlated and E)
differ only slightly from a problem weve already solved (HF and
E).
The energy is calculated to various orders of approximation.
Second order MP2; Third order MP3; Fourth order MP4...
Computational cost increases strongly with each succesive
order.
At infinite order the energy should be equal to the exact solution
of the S.E. (for the given basis set). However, there is no
guarantee the series is actually convergent.
In general only MP2 is recommended
MP2 ~ including all single and double excitations

Coupled Cluster (CC) Theory

An exponential operator is used in constructing the expansion of

determinants.
Leads to accurate and compact wave function expansions yielding
accurate electronic energies.
Common Variants:
CCSD: singles and doubles CC
CCSD(T): CCSD with approximate treatment of triple
excitations. This method, when used with large basis sets, can
generally provide highly accurate results. With this method, it is
often possible to get thermochemistry within chemical accuracy,
1 kcal/mol (4.184 kJ/mol)

Frozen Core Approximation

In general, only the valence orbitals are involved in
chemical bonding.
The core orbitals dont change much when atoms are
involved in molecules than when the atoms are free.
So, most electronic structure calculations only correlate
the valence electrons. The core orbitals are kept frozen.
i.e., 2s and 2p electrons of Oxygen would be
correlated, and the 1s electrons would not be
correlated.

Density Functional Theory

The methods weve been discussing can be grouped together
under the heading Wavefunction methods.
They all calculate energies/properties by calculating/improving
upon the wavefunction.
Density Functional Theory (DFT) instead solves for the electron
density.
Generally computational cost is similar to the cost of HF
calculations.
Most DFT methods involve some empirical parameterization.
Generally lacks the systematics that characterize wavefunction
methods.
Often the best choice when dealing with very large molecules
(proteins, large organic molecules...)

The type of calculation of Gaussian software

1. The job type: Energy, Optimization, Frequency (for IR and Raman), NMR
2. The method
3. The basis set

2. The Method:
Hartree-Fock Calculations
CCSD Coupled Cluster method with single and double clusters
MP2,MP4 Moller-Plesset method
DFT Density Functional Method
CASSF Complete Active Space SCF (self-consistent field)
CIS: Configuration interaction with single-excitations
TD-SCF: time-dependent SCF (self-consistent field) for UV-Vis calculations

Basis Sets

Basis sets determine the number

of functions used to describe the
electronic structure. A simple
example is the best way to get
started.

Say I have a shape I want to describe, for example a car as in the

diagram. I could describe this shape with a single basis function (a
circle). If I use only one basis function (a circle) of a given size, the
shape of the car is not well reproduced. However, if I allow my circles
to vary slightly in size, ie if I increase my basis set to two functions I
get a better fit, and if I allow even more functions I can describe the
shape of the car very well! If we add too many basis functions the
calculation will take too long, so we always have to balance
computational difficulty vs the size of the basis set.

Basis Set Approximation:LCAO-MO

1 (1) 1(1) 2 (1)K
1 1 (2) 1 (2) 2 (2)K
0
N! L
L
L
1 (N ) 1(N) 2 (N )K

M (1)
M (2)
L
M (N)

Slater determinants are built from molecular orbitals, but how do

we define these orbitals?
We do another expansion: Linear Combination of Atomic
Orbitals-Molecular Orbitals (LCAO-MO)
M

i c ki k
k

Molecular orbital coefs, cki, determined in SCF procedure

The basis functions, i, are atom-centered functions that
mimic solutions of the H-atom (s orbitals, p orbitals,...)
The larger the expansion the more accurate and expensive the
calculations become.

H-atom eigenfunctions correspond to

hydrogenic atomic orbitals.
l=0
m=0

z
y
x

l=1
m=-1

m=0

l=2
m=+1

n=1

1s

n=2

2s

2px

2py

2pz

n=3

3s

3px

3py

3pz

m=-2,-1,0,1,2

3d orbitals (5)

Construct each MO i by
LCAO.
Lennard-Jones (1929) proposed treating
molecular orbitals as linear combinations
of atomic orbitals (LCAO):

i Ci i
i 1

Linear combination of s orbital on one atom with s or p

orbital on another gives bond:
Linear combination of p orbital on one atom with p orbital
on another gives bond:

Gaussian Type Orbitals

The radial dependence of the H-atom solutions are Slater type functions:

n1 r
Most electronic
theory
calculations
(whateweve been talking
structure
(r,

NY
(

)r
,n,l ,m
l,m
about) use Gaussian type functions because they are computationally
much more efficient.

ly

,l x ,ly ,lz (x,y,z) Nx y z e

lx

lz

r 2

Gaussiantypefunction
Slatertypefunction

0.8
0.6
0.4

lx + ly + lz = l and determines type of orbitals (l=1 is a p...)

s can be single Gaussian functions (primitives) or themselves
be linear combinations of Gaussian functions (contracted).
0.2

Minimal basis sets

The most common minimal basis set is STO-nG,
where n is an integer. This n value represents the
number of Gaussian primitive functions comprising a
single basis function.

Types of Basis Sets

Minimal: One basis function (STO, GTO, or CGTO) for each
atomic orbital in the atom
Double-zeta: Two basis functions for each AO
Triple-zeta: Three basis functions for each AO
... and etc. for quadruple-zeta (QZ), 5Z, 6Z, ... Having
different-sized functions allows the orbital to get bigger or
smaller when other atoms approach it
A split-valence basis uses only one basis function for each
core AO, and a larger basis for the valence AOs

Pople-style basis sets

Named for Prof. John Pople who won the Nobel Prize in
Chemistry for his work in quantum chemistry (1998).
Notation:
631G
Use6primitives
contractedtoasingle
contractedGaussian
todescribeinner(core)
electrons(1sinC)

Use2functionsto
describevalenceorbitals(2s,2pinC).
OneisacontractedGaussian
composedof3primitives,
thesecondisasingleprimitive.

6311G

Use3functionstodescribevalenceorbitals...

631G*

Addfunctionsofang.momentumtype1greaterthan
occupiedinbondingatoms(ForN2wedaddad)

631G(d)

Sameas631G*for2ndand3rdrowatoms

Diffuse Functions
Diffuse functions have small exponents; this means
the electron is held far away from the nucleus
Necessary for anions, Rydberg states, very
electronegative atoms (fluorine) with a lot of electron
density
Necessary for accurate polarizabilities or binding
energies of van der Waals complexes (bound by
dispersion)
It is very bad to do computations on anions without
using diffuse functions; your results could change
completely!

 Allow size variation.

Contracted
limit

Diffuse
limit

Adjusted
size

Double-zeta
basis set
or more
(cc-pV5Z)

Alternatively, use size adjustment only for

outermost electrons (split-valence set) to
speed calculations.
For example, in the 6-31G set:
Inner orbitals of fixed size based on 6 primitives
each.
Valence orbitals with 3 primitives for contracted
limit, 1 primitive for diffuse limit.

Additional very diffuse limits may be added

(e.g., 6-31+G or 6-311++G).

Polarization functions
Usually achieved by mixing orbital types:
p

For example, consider the 6-31G(d,p) or 6-31G** set:

Add d polarization to p valence orbitals, p character to s
Can build complicated sets: 6-311G(3df,2pd)
As other atoms approach, an atoms orbitals might want
to shift to one side or the other (polarization). An s orbital
can polarize in one direction if its mixed with a p orbital.
p orbitals can polarize if mixed with d orbitals
In general, to polarize a basis function with angular momentum,
mix it with basis functions of angular momentum l + 1

Computational Cost
Method
HF
MP2
CCSD
CCSD(T)

ScalingofCost
M2M3
M5
M6
M7

Why not use best available correlation method with the largest
available basis set?
A MP2 calculation would be 100x more expensive than HF
calculation with same basis set.
A CCSD(T) calculation would be 104x more expensive than
HF calculation with same basis set.
Tripling basis set size would increase MP2 calculation 243x
(35).
Increasing the molecule size 2x (say ethanebutane) would
increase a CCSD(T) calculation 128x (27).

Jacob ladder

Improved electron correlation

H-F MP2

MP4 QCISD(T) ... Full CI

STO-3G
3-21G

More
complete 6-31G(d)
basis
6-311G(d,p)
sets

6-311+G(d,p)
Infinite basis
set

Exact
solution