Introduction to Computational Quantum

Chemistry
 Definition of Computational Chemistry
• Computational Chemistry: Use mathematical
approximations
pp and computer
p programs
p g to obtain results
relative to chemical problems.
• Computational Quantum Chemistry: Focuses specifically
on equations
ti andd approximations
i ti derived
d i d from
f the
th
postulates of quantum mechanics. Solve the Schrödinger
equation for molecular systems.
• Ab Initio Quantum Chemistry: Uses methods that do not
include any empirical parameters or experimental data.
 What’s it Good For?

• Computational chemistry is a rapidly growing field in chemistry.

– C
Computers
t are getting
tti faster.
f t
– Algorithims and programs are maturing.
• Some of the almost limitless pproperties
p that can be calculated
with computational chemistry are:
– Equilibrium and transition-state structures
– dipole and quadrapole moments and polarizabilities
– Vibrational frequencies, IR and Raman Spectra
– NMR spectra
– Electronic excitations and UV spectra
– Reaction rates and cross sections
– thermochemical data
 Motivation

• Schrödinger
g Equation
q can onlyy be solved exactlyy for simple
p
systems.
– Rigid Rotor, Harmonic Oscillator, Particle in a Box, Hydrogen Atom
• F
For more complexl systems
t (i.e.
(i many electron
l t atoms/molecules)
t / l l )
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).
– IIn general,
l the
th ““cost”
t” off the
th calculation
l l ti increases
i with
ith the
th accuracy off the
th
calculation and the size of the system.
 Getting into the theory...
• Three parts to solving the Schrödinger 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”
Method

– Representation of Slater determinants by molecular orbitals, which

are linear combinations of atomic-like-orbital functions.
functions
• The basis set
The Born-Oppenheimer Approximation
 Time Independent Schrödinger Equation
• We’ll be solving the Time-Independent Schrödinger Equation

Hˆ ψ = Eψ
Hˆ = Tˆ + Vˆ Or written as: Hˆ = Eˆ kinetic + Eˆ potential

For Many electron atoms/molecules:

2
1 2 2
Zα Zβ e ′ 2 Zα e′ 2 e′ 2
H=− ∑
ˆ ∇ − ∑∇ + ∑ ∑
2
− ∑∑ + ∑∑
2 α mα α 2me i
i
α α β > rαβ α i riα j i > j rij

Nuclei Electron Nuclear- Nuclear- Electron-

kinetic kinetic Nuclear electron electron
energy energy repulsion
li attraction
tt ti repulsion
li

Tˆ Vˆ
⎛ − 2 d2 ⎞
∇i ≡ ∂ ∂ ∂
2 2 2
2 + 2 +
2
⎜ ⎟ where:
∂x ∂y ∂z
2
⎝ 2m dx 2 ⎠
 The Born-Oppenheimer Approximation
• The wave-function of the many-electron molecule is a
function of electron and nuclear coordinates: ψ((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:
ψ(R,r)=
(R r)= ψel(r;R) ψN(R)
 Electronic Schrödinger Equation
• Now we can solve the electronic part of the Schrödinger
equation
q separately.
p y Diatomic Potential Energy Surface (HgBr)
12
Hˆ elψ el (r; R) = E elψ el (r; R) U(R)
8

′ ′
2 2 2 4
Z e e
Hˆ el = − ∑ ∇ − ∑∑ α
2
+ ∑∑

U(R) ((kcal/mol)
i Re
2me i α i riα j i > j rij
0

-4
• BO O approximation
i i leadsl d De
-8

to the idea of a potential

-12

energy surface.
surface -16

U(R) = E el + VNN -20

3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Zα Zβ e′ 2
R (a0)
VNN = ∑ ∑
α α >β rαβ Atomic unit of length
1 bohr = 1 a0 = 0.529177 Å
 Nuclear Schrödinger Equation
• Once we have the Potential Energy Surface (PES) we can
solve the nuclear Schrödinger equation.
Hˆ ψ (R) = E ψ (R)
N N N N
2
1 2
ĤN = −
H ∑ ∇ + U (R)
2 α mα α Vibrational Energy Levels of HF
50000

v=17
• Solution of the nuclear SE 40000

allow us to determine a large

R) (cm-1)
30000
variety of molecular properties.
A example
An l are vibrational
ib ti l U(R 20000

energy levels. v=3

10000
v=2
v=1
v=0
0
1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
R (a0)
Polyatomic Potential Energy Surfaces
Thermal Rate Coefficients
O + HCl → OH + Cl
10-12 Data Points from experiment

k (cm-3 moleculess-1)
10-13

PES1
10-14

10-15

10-16
PES2
-17
10
0.0005 0.0015 0.0025 0.0035

1/T (K-1)
0.060
0.030

1.5

2.0

2.5

0 r (OH),
3.0
20
bohr
40 3.5 • We can only look at cuts/slices
r(OCl)=4.99 a0
60
4.0
• 3n-6 degrees of freedom
80
Theta (HOCl), 100
• Minima
Mi i and dTTransition
iti states
t t
4.5
degrees 120 • Minimum energy path
• Like following a stream-bed