Semi-empirical and Density

Functional Theory Methods

Computational Chemistry 5510

Spring 2006 Hai Lin
 Practice with HF Theory
•Computational cost ~ N4 (N is the number of basis sets)
STO-3G 6-31G 6-31G* 6-31G**
H 1 2 2 5
C 5 9 15 15
C6H6 36 66 102 120

•Accuracy is limited (not account for electron correlation)

Two electrons having the same spins avoid

each other. (Accounted for by the
Slater determinant) e- e-

Two electrons having the opposite spins

avoid each other. (Not considered)
 Correlate Electrons
HF Theory

Implicit Electron Explicit Electron

Correlations Correlations

Semi-empirical Electron-Correlated
Wave Function Methods Wave Function Methods

•Møller-Plesset Perturbation Theory

AM1, PM3, MNDO, etc. MPn (n = 2, 3, 4…)
•Configuration Interaction Methods
Full CI, CISD, MRCI, etc.
•Coupled Cluster Methods
CCSD, CCSD(T), etc.
 Semi-empirical Methods
• Employing simplifying assumptions when solving Hartree-Fock
(actually Roothaan-Hall) equations.

• The simplifications neglect certain integral terms that are

expensive to calculate, and rely on empirically parameters to
make calculations in agreement with experimental data.
(That is why these methods are called semi-empirical methods.)

• The parameterization HF Theory

procedure accounts for
electron correlations
implicitly. Additional
Approximations
• Scaling behavior: N3
Semi-empirical
Methods
Common Semi-empirical Methods
• 1965 Pople CNDO
• 1967 Pople INDO
• 1975 Dewar MINDO/3
• 1977 Dewar MNDO
• 1985 Dewar AM1
• 1989 Stewart PM3
• 1970’s Zerner ZINDO
• 1996 Thiel MNDO/d

• Accuracy depends on parameterizations and can not be

systematically improved (like molecular mechanics).
• Validate the method before using it.
• Applied to molecules of relatively large size (~ 300 atoms).
• Obtain preliminary results that are refined by high-level calculations.
 Extended Hückel Theory
• Most semi-empirical methods above make approximations at the
integral level, i.e., neglecting certain integral terms when calculating
the Fock matrix.

• Extended Hückel Theory (EHT) makes approximation directly on

the Fock matrix elements, and again needs parameterization.

• EHT is often used to provide an initial guess for the orbitals that are
used in higher-level (e.g., HF and DFT) calculations.

• Originally developed by Hoffmann et al. in 1960s. Recently, it

becomes hot again for treating large systems, especially in studies
of proteins containing metals, and is called “tight-binding” theory.
 What is a Functional?
• A function depends on a set of variables.

y = f (x)
E.g., wave function depend on electron coordinates.

• A functional depends on a functions, which in turn

depends on a set of variables.

E = F [ f (x) ]
E.g., energy depends on the wave function, which
depends on electron coordinates.
 Density Functional Theory

• The electron density is the square of wave
function and integrated over electron
coordinates.

• The complexity of a wave function increases

as the number of electrons grows up, but the x
electron density still depends only on 3
coordinates.

• 1964 Hohenberg & Kohn 

• The ground-state electronic energy is determined
completely by the electron density .

E = F [  (x) ]
• If we knows electron density , we can bypass
the wave function and calculate energy directly! x
 Density Functional Theory (2)
• There is a one-to-one connection between energy E and density  :
E = F [  (x) ], but we do not know the F! (A trade-off!)
The central task in DFT is to find the F.

• Thomas-Fermi-Dirac Model: Non-reacting uniform electron gas

• Kohn-Sham Theory (1965): Atoms & Molecules

EDFT[] = T[] + Ene[] + J[] + Exc[]

electrons-electrons
Electronic Exchange energy
Kinetic energy electrons-electrons
Coulombic energy
Nuclei-electrons
Coulombic energy
 Density Functional Models
• The central task in DFT is to find the functional that is as accurate
as possible. (Maybe we will never know the exact functional…)

Various functions proposed whose coefficients are adjusted to obtained

agreements with experiments or high-level ab intio calculations

• Local Density Approximation (LDA)

• Assuming the functional depends only on the electron density
• Example: LSDA (e), VWN (c)

• Gradient Corrected or Generalized Gradient Approximation (GGA)

• Assuming the functional depends on both the electron density
and its gradient
• Examples: PW86 (e), B88 (e), PW91 (c), LYP (c), BLYP

(e = exchange, c = correlation)
 Density Functional Models (2)
• Hybrid Models
• Take the exchange as a linear combination of terms from LSDA,
Hartree-Fock, and GGA.
• Example: HH (e), B3 (e), B3LYP

• Doubly Hybrid Models

• In addition to mix the exchange with Hartree-Fock exchange, also
mix the correlation with MP2 correlation.
• Examples: MC3MPW, MC3BB

• Meta-GGA Models
• Assuming the functional depends on both the electron density
and its gradient (GGA) as well as kinetic energy density.
• Examples: VSXC, BB95
 Which DFT Models to Use?
• DFT scaling behavior ~ N4
• Slightly more expensive than HF but more accurate
• No systematic way to improve the accuracy (at least up till now).

• Accuracy varies from model to model, and from one application

area to another.
• BLYP good for metals, poor for organic compounds
• B3LYP poor for metals, good for organic compounds
• MPW1K specially parameterized for kinetics (good for transition
states and reaction barrier heights, poor for stable
molecules)
• Commonly regarded as poor for H-bonding and weak (dispersion)
interactions, but some people disagree.

• Validate a model before use it.

• Test the model on small molecules where reliable experimental data are
available or high-level ab intio calculations can be done.
 Koopman’s Theorem
• Frozen MO assumption: The molecule orbitals are constant for a
given neutral molecule and its ions (anion and cation)

• For a neutral molecule:

• Ionization energy = occupied orbital energy
• Electron affinity = unoccupied orbital energy
(It is better to calculate electron affinity as occupied orbital energy
in the anion.)
E
Unoccupied

Occupied
 Restricted & Unrestricted HF
• Electrons have spins ( and , or up and down). To identify an
electron, both spatial orbitals and spin orbitals are required.
• Restricted HF: accommodate electrons of opposite spins in pairs
(i.e., in the same spatial orbitals).
• Unrestricted HF: allow two electrons of opposite spins staying in
different spatial orbitals.
E 
Unoccupied

Occupied

Closed shell Open shell Open shell

RHF (singlet) ROHF (doublet) UHF (doublet)
 Unrestricted HF
• For a closed-shell system, UHF and RHF gives the same results.
• For an open-shell system, UHF gives lower energy than RHF
(ROHF) does, because the system is now relaxed from the
restriction of forcing  and  electrons in the same spatial orbitals.
• A hydrogen molecule
dissociates into ... E
H+ H-
• UHF: two atoms
• RHF: two ions (becuase R
the  and  electrons
have to be in the same
H H
spatial orbitals even if
two nuclei are far away
from each other).
H2
 Problems with UHF
• For an open-shell system, UHF has the spin contamination
problem: The UHF wave function is not an eigenfunction of the S2
operator (S is the electron spin operator).
• For example, a singlet UHF wavefunction will have contributions
from triplet and other high-lying states. (Not physical!)
• If such a contribution is small, i.e., S2 is close to 0.75, the
wavefunction is approximately right.
• If such a contribution is large, e.g., S2 is much larger than 0.75,
the wavefunction is qualitatively wrong, and the calculation is
meaningless.
 Valence Bond Theory
• Close to simple chemical bonding concept: two electrons pair to
form a valence bond.
Seperated far away:  = A() B()

A R B

Bonding:   A() B() + A() B()

Problems:
A B A B • Lack of ionic character
— dissociation only into
neutral fragments
• Orbitals are non-orthogonal
A- B+ A+ B- — complications in
calculations, making it far
less popular than
molecular orbital theory
 Summary

• Problems with HF theory

• Semi-empirical theory
• Density functional theory
• Koopman‘s theorem
• Restricted HF vs. Unrestricted HF
• Valence Bond Theory
 Your Homework
• Read the slides. If you have difficulty in understanding the math in the
slides, find a reference.
• Read textbook (Take notes when you read.)
• §3.4, §3.7, §3.8.4, §3.9, §3.10, §3.11, §3.12, and §3.13. You can
skip the math in §3.9 and §3.10.
• §6.1 - §6.5. You can skip the math in those chapters.
• Questions:
1.Why is it better to calculate the electron affinity from an anion
than from a neutral molecule?
2.What is a RHF? What is a UHF? What is the potential problem
of using UHF?
3.What are the advantages of using semi-empirical and DFT
methods?