Quantum Chemistry

Jan G. Korvink and Evgenii Rudnyi

IMTEK
Albert Ludwig University
Freiburg, Germany

ALBERT-LUDWIGS-
UNIVERSIT T FREIBURG

Learning Goals
♦ Where the potential function
comes from: Adiabatic approxi-
mation
♦ Molecular orbitals and the
Hartree-Fock equation
♦ Designing molecular orbitals -
LCAO
♦ Electron correlation
♦ State of the art
References
♦ Leach, A.R., Molecular modelling:
principles and applications.
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation
Preliminaries
On-line resources
♦ On-line book: Jack Simons,
Quantum Mecha-nics in
Chemistry, simons.hec.utah.edu/
TheoryPage/index.html
Tutorials
♦ Neal McDonald et al, An Intro-
duction to Quantum Mechanics
www.chemistry.ohio-state.edu/betha/
qm/
♦ C. David Sherrill, Lectures in
Quantum Chemistry,
vergil.chemistry.gatech.edu/notes/
index.html
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UNIVERSIT T FREIBURG
 Potential Energy Surface
♦ Time-dependent and stationary
Schrödinger equation AB + C = A + BC
♦ Molecular Hamiltonian
♦ Separating electronic and
nuclear wavefunctions:
Born-Oppenheimer approxi-
mation
♦ Example: Chemical Reaction
Path

from Atkins

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG

Schrödinger Equation
dΨ
♦ Time-dependent HΨ = ih
dt
♦ H - Hamiltonian operator,
h = h ⁄ 2π
♦ Ψ ( r, t ) - wave function,
Ψ ( r, t ) - probability density ♦
2
♦ Separation for time and space
variation
♦ Potential energy is
independent of time.
♦ Ψ ( r, t ) = ψ ( r )θ ( t )
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation
Potential Energy Surface
♦ Stationary equation
Hψ = Eψ
♦
Number of discrete states
{ψ i, E i}
♦ Ab initio - From the first
principles - Based on a limited
number of experimental results.
All interatomic forces can be
explained from the Coulomb
law.
♦ We do not have potential
surface yet.
♦ Energy does not depent on
atom positions.
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 Potential Energy Surface
Molecule Hamiltonian Nuclei ( R ) and electrons ( r ) :
Ψ ( R, r )
www-
wilson.
ucsd.
edu/
educa-
tion/

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Potential Energy Surface
Born-Oppenheimer ♦ E el ( R ) is the nuclei potential
energy.
Approximation ♦ Schrödinger equation for nuclei
♦ Proton is 1836 times heavier
H nuc ( E el )Ψ ( R ) = E nuc Ψ ( R ) .
than electron.
♦ Factorize for nuclei part ♦ Non-adiabatic coupling is
neglected (typically this is a
Ψ ( R, r ) = Ψ ( R )ψ ( r ;R ) .
small term).
♦ Schrödinger equation for
♦ Usually people solve the
electrons
electonic equation only.
H el ψ ( r ;R ) = E el ( R )ψ ( r ;R ) .
♦ Nuclei movements is treated
♦ This is parametric equation by the clasical mechanics.
over nuclei coordinates.
♦ Quantum chemistry solves
the electronic equation.

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Potential Energy Surface
Example - Chemical ♦ Demonstration from
scsg9.unige.ch/fln/eng/toc.html
Reaction Path

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Molecular Orbitals and HF SCF
♦ Atomic units

♦ Variation Principle

♦ Molecular orbitals Simulated STM images for an arsenic vacancy

on the (110) surface of GaAs.
www-users.cs.umn.edu/~saad/projects/DMR/
page4_rt.htm
♦ Hartree-Fock Self Consistent
Field (HF SCF)

♦ Language For Chemists

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG

Atomic Units
♦ 1 unit of charge is the electron
-19
charge|e|=1.60219x10 C.
♦ 1 unit of mass is the electron
mass me = 9.10593x10-31 kg.
♦ 1 unit of length (1 Bohr) is
2 2 2 – 11
a o = h ⁄ 4π m e e = 5.29177 × 10 m
♦ h = 2π , h = 1
♦ 1 unit of energy (1 Hartree) is
2 – 18
E a = e ⁄ 4πε o a o = 4.35981 × 10 J
♦ 1 Hartree = 2.63 MJ/mol =
27.3 eV
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation
HF SCF
♦ Zero energy is nuclei and
electrons separated at
infinity.
♦ Dissociation energy is a small
difference of huge numbers.
♦ Example (GAMESS + sim-
ple HF):
♦ Cl2: E el = -918.9371
♦ Cl: E el = -459.4734
♦ 2Cl: E el = -918.9468
♦ Cl2 = 2Cl ∆E = 0.0097 = 25
kJ/mol.
♦ Experimental: 240 kJ/mol.
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 HF SCF
Variation Principle ∫
*
Ψ trial HΨ trial dx
ε = ----------------------------------------
- over
∫ Ψtrial Ψtrial dx
*
Electronic Hamiltonian
n n N n unknowns
ZI 1 1
♦ – --- ∑ ∇ i – ∑ ∑ ----- + --- ∑ -----
1 2
2 r Ii 2 r ij ♦ For any Ψ trial ε ≥ E o
i i I i, j
without nucleus-nucleus
repulsion
Variational theorem
♦ Choose a trial wavefunction,
Ψ trial with unknown param-
eters
♦ Minimize Reyleigh ratio

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 HF SCF
Molecular Orbitals Electron has spin: +1/2 or
Ψ ( 1, 2, …, N ) = χ 1 ( 1 )χ 2 ( 2 )…χ N ( N ) -1/2
♦ Does not work - breaks indis- ♦ Closed shells: Restricted
tinguishability criterion Hartree-Fock (RHF) - Each
space MOs holds two electrons.
Slater determinant ♦ Open shells (odd number of
electrons)
χ1 ( 1 ) χ2 ( 1 ) … χN ( 1 )
♦ Restricted Open Shell HF
1 χ ( 2 ) χ2 ( 2 ) … χN ( 2 ) (ROHF) - Just few space MOs
♦ Ψ = -------- 1
N … … … … holds one electron.
χ1 ( N ) χ1 ( N ) … χN ( N ) ♦ Unrestricted HF (UHF) - Each
space MO holds one electron.
♦ Satisfies antisymmetry
principle

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 HF SCF
Hartree-Fock Self ♦ A system of coupled non-
linear integral-differential
Consistent Field equations
♦ Substitute the Slater deter- ♦ Iterative solution: start with
minant into Reyleigh ratio. The some χ i , compute f i , solve
minimum is given by
for new χ i , and so on.
Hartree-Fock ♦ Introduces a lanquige for
chemists.
Equations ♦ But this is just an approxi-
♦ fi χi = εi χi mation.
♦ f i - Fock operator (depends
on all the molecular orbitals)
♦ ε i - Molecular orbital energy

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 HF SCF
Language For Molecular Orbital
♦ LUMO - Lowest Unoccupied
Chemists Molecular Orbital
♦ HOMO - Highest Occupied

♦ HOMO and LUMO of

formamide from Leach’s book

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 LCAO
♦ Linear Combination of Atomic
Orbitals (LCAO)

♦ Visualizing 3d atomic orbital

♦ Roothan-Hall Equations

♦ Basis set Electronic charge density of silicon in the dia-

mond structure.
www-users.cs.umn.edu/~saad/projects/DMR/
page4_rt.htm
♦ Semi-empirical methods

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 LCAO
Molecular Orbitals cmj.

Closed shells Atomic orbitals

♦ For each pair of two spin ♦ Solving Schrödinger equation
for the atom (1s, 2s, 2p, 3s, 3p,
orbitals χ i = ϕ j α and
3d, ...).
χi + 1 = ϕj β . ♦ K atomic basis functions
♦ For open shells there are more produces 2K spin orbitals.
problems, see textbooks. ♦ N electrons, then there are 2K-N
Linear Combination of unoccupied orbitals.
♦ Typically for large molecular
Atomic Orbitals systems K >> N.
K
♦ ϕj = ∑ cmj φm unknowns are
m

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 LCAO
Visualizing 3d Orbital ♦ Isosurfaces and slices

(http://www-wilson.ucsd.edu/
education/)

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG

Roothan-Hall
Equations
♦ Substitute LCAO for molecular
orbitals in the Hartree-Fock
equations - for the closed shell
the solution is given by a matrix
equation
♦ FC = SCE
♦ F - Fock matrix: obtained
from the different integrals
over basis functions, number
of integrals
(K4+2K3+3K2+2K)/8
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation
LCAO
♦ S - overlap matrix: to make
molecular orbitals
orthogonal
♦ C - matrix with unknowns in
LCAO
♦ E - diagonal matrix with
molecular orbital energies
♦ F and S depends on C. The
solution is again iterative: start
with some C, compute F and S,
then compute new C and E, and
so on.
♦ Fortunately non-linearity is
rather weak.
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UNIVERSIT T FREIBURG
 LCAO
Basis Set ♦ Still, computing integrals
takes too much time
♦ Slater Type Orbital (STO)
♦ Gaussian Type Orbitals (GTO)
♦ Radial part 2
n – 1 – ar j j k – ar
ψ ( r ) = Ar e (already ♦ ψ ( r ) = Ax y z e (very
some approximation) fast to compute integrals)
♦ Equilibrium bond length of H2
STO-3G 4-31G 6-31G* 6-31G** Expr.
1.346 1.380 1.380 1.385 1.401
(atomic units)

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 LCAO
Comparison of Basis Sets
♦ ,
1997 www.emsl.pnl.gov:2080/docs/tms/abinitio/cover.html

number of C

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 LCAO
Semi-Empirical Neglect of differential
Methods overlap
♦ CNDO - complete neglect,
Simplifying computing INDO - intermediate neglect,
♦ Leave Roothan-Hall equations MINDO - modified interme-
♦ Take into account valence diate neglect, MNDO - modified
electrons only, ignore core neglect
electrons ♦ AM1 - Austin model 1
♦ PM3 - Parametrization 3
♦ Neglect some integrals
The zero energy is differ-
♦ Parametrize the other integrals
from experimental values ent.

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Advanced Quantum Chemistry
♦ Electron correlation

♦ Configuration Interaction

♦ Density Functional Theorem

♦ Summary
Quantum Dot calculation (more than 1000
atoms)
♦ Relativistic corrections http://www-users.cs.umn.edu/~saad/
projects/DMR/page2_rt.htm

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Advanced QC: Electron Correlation
♦ Hartree-Fock is a mean field ♦ As a result, for two electrons
theory P ( r 1, r 2 ) = P ( r 1 )P ( r 2 )

Peter Knowles

http://www.fz-juelich.de/nic-series/Volume3/Volume3.html

♦ Overestimate ionic states at long find two electrons close together

distances and the probability to

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Advanced Quantum Chemistry
Configuration Moller and Plesset
Interaction (CI) perturbation theory
♦ K basis functions produces 2K ♦ H = H o + λV
spin orbitals. ♦ MP2, MP3, MP4, for example,
♦ N electrons, then there are 2K-N MP2/6-31G*
unoccupied orbitals.
♦ CI:
Ψ = c0 Ψ0 + c1 Ψ1 + c2 Ψ2 + …
♦ Number of configurations is
(2K!)/[N!(2K-N)!].
♦ CIS, CID, CISD, however they
are not size consistent.

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Advanced Quantum Chemistry
Density Functional ♦ F is some functional (unfortu-
nately not known).
Theory ♦ Kohn & Sham (1965) suggested
♦ Hohenberg & Kohn, 1964. some empiric approximation for
♦ Ground-state energy is F.
uniquely defined by the electron ♦ LDA - local density approxi-
density mation.
E ρ ( r ) = V ( r )ρ ( r ) dr + F ρ ( r ) . ♦
∫ ext
BLYP - Becke-Lee-Yang-Par
gradient-corrected functional.
♦ ρ is the electron density. ♦ Roughly speaking: to take into
♦ V is the external potential account the electron correlation
(Coulomb interaction with for for a single HF computation.
nuclei).

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Advanced Quantum Chemistry
Summary

Mark S. Gordon
Tutorial for GAMESS

www.msg.ameslab.gov/Group/
GroupTutor.html

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Advanced QC: Relativistic effects
♦ In principle, it is necessary to Dirac equation - a set of four
solve not Schrödinger but rather coupled differential equations

M. Dolg, www.fz-juelich.de/nic-series/
Volume3/Volume3.html

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Current State of The Art
♦ A - Ethylene, 16 electrons, Basis functions)
Set = 6-311++G** (74 functions) ♦ C -18-crown-6, C12H24O6, 144
♦ B - Ethylene, 16 electrons, 6- electrons - 606 functions
311++G(3df,3pd) (150
A B C
RHF 8 45 90197
RHF-gradient 14 133
RHF-gessian 56 789
MP2 11 481
MP4 83
CISD 46

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Software
Commercial Lists
♦ GAUSSIAN: ♦ www.ch.ic.ac.uk/local/
www.gaussian.com/ organic/mod/software.html
♦ CACHE:
www.cachesoftware.com
♦ Materials Studio:
www.accelrys.com
Free
♦ General Atomic and Molecular
Electronic Structure System
(GAMESS)
www.msg.ameslab.gov/
GAMESS/

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG
 Summary
♦ Where the potential function
comes from: Adiabatic approxi-
mation

♦ Atomic and molecular orbitals

♦ Multi-electron systems:
Hartree-Fock equation

♦ Electron correlation: Configu-

ration Interaction

♦ Current state of the art

ALBERT-LUDWIGS-
E.B. Rudnyi, J.G. Korvink, Chair for Microsystem Simulation UNIVERSIT T FREIBURG