Semi-Empirical Methods:

Introduction
• Computational chemistry is one of the
fastest growing areas of chemistry

• Used to computationally determine vital

information • Geometry
– Bond Angles, Bond
Distances, Dihedral
Angles
• Dipole Moment
• Enthalpy of Formation
• Ionization Potentials
 Electronic Structure
• Calculations based on determining electronic
structures

• Different Approaches:
– Density Functional Theory
– Ab Initio
– Semi-empirical
 Semi-Empirical Methods

• Some of the electrons are considered

explicitly

• Reduces computational demand of the

problem

Pilar, F.L. Elementary Quantum Mechanics. Second Edition. Dover

Publications, Inc. Mineola, New York, 1990, 454.
 Semi-Empirical Approximations
• “Ignoring” of core electrons
– Core electrons reduce nuclear charge
– Introduction of function to model combined
repulsion due to nuclei and core electrons
• Minimum basis set of functions to account
for valence electrons
– Majority of basis functions are taken to be
STOs
Jensen, F. Introduction to Computational Chemistry. John Wiley & Sons,
England 1999, 81.
 Huckel Approximations
• 1931, E. Huckel showed depiction of
conjugated hydrocarbons by use of quantum
mechanical model which only considered pi
electrons.

-C=C–C=C–C=C-
• Applicable to chain and cyclic conjugated
systems
 Central Assumption
• Zero Differential Overlap approximation
– Neglects all products of basis functions depending
on the same electron coordinates when located
on different atoms
• How many integrals are neglected is which
determines the various Semi-Empirical
methods

Jensen, pg 81
Neglect of Diatomic Differential Overlap
(NDDO)

• Only uses the previously mentioned central

assumption
• Overlap Integral

Sm = < mA| B > = dmvdAB

Jensen, pg 82
 Intermediate Neglect of differential
Overlap (INDO)
• In addition to NDDO:
– Neglects all two-centre 2 electron integrals which
are not of the Coulomb type
– To preserve rotational invariance, some integrals
must be made independent of orbital type

Jensen, pg 83
 Complete Neglect of Differntial Overlap
(CNDO)
• Only the Coulomb one-centre and two-centre
2 electron integrals remain:

< mAnB | lCsD> = dACdBDdmldns < mAnB | mAnB>

< µAnB | µAnB> is independent of orbital type (s or p)

Jensen, pg. 83
 Parameterization
• Direct use of ZDO approximations is not useful
due to only qualitative picture of MOs
• 3 Methods to transform NDO approximations
into useful computational models
1) Remaining integrals calculated from functional form
of AO’s
2) Remaining integrals made into parameters, assigned
values based on experimental data
3) Remaining integrals made into parameters, assigned
values based on fitting to experimental data

Jensen, pg. 84
 Modified NDDO Models
• MNDO

• AM1

• PM3
 Modified Neglect of Diatomic Overlap
(MNDO)
• One of first paramaterization models used
– Parameterizes: H, B, C, N, O, F, Al, Si, P, S, Cl, Zn,
Ge, Br, Sn, I, Hg, and Pb.
• Some Limitations
• Succeeded by AM1 and PM3 Models

Jensen, pg. 87
 Austin Model 1 (AM1)
• Developed by Dewar at the University of Texas
at Austin, 1985.
• Came from systematics errors of MNDO
– Too high repulsion between atoms 2-3 Å apart
• Parameterized for:
– H, B, C, N, O, F, Al, SI< P, S, Cl, Zn, Ge, Br, I, and Hg.
• Some Limitations

Jensen, pg. 87
 AM1
- Heats of Formation (kcal/mol )
- 1,4-pentadiene: 25.2 (expt), 25.0 (Dewar), 25.2
(CAChe)
- MNDOd calculations yielded 26.0
- 2-propyl cation: 192 (expt), 192 (Dewar), 208
(CAChe)
- Ammonium: 155 (expt), 151 (Dewar), 151
(CAChe)
 AM1 Geometries
• Ethene • Furan
– CC 1.339 1.326 – OC1 1.362 1.431
– CH 1.086 0.964 – C2C3 1.361 1.526
– HCC 121.2 114.64 – C3C4 1.431 1.522
• Nitrogen – C2H 1.075 1.121
– NN 1.094 1.106 – C3H 1.077 1.117
– HC2O 115.9 107.2
– HC3C4 128.0 111.2
 Modified Neglect of Diatomic Overlap,
Parametric Method Number 3 (PM3)
• MNDO and AM1 parameters were done by hand,
limiting number of reference compounds
• Essentially, AM1 with all parameters fully optimized
• Still needs some human intervention
• Parameterized for:
– H, Li, C, N, O, F, Mg, Al, Si, P, S, Cl, Zn, Ga, Ge, As, Se, Br, Cd,
In, Sn, Sb, Te, I, Hg, Tl, Pb, Bi, Po, and At
– Additional transition metals are being developed to
include d orbitals
 Limitations
• ~1000 atoms, due to diagonzalization of Fock
matrix
• Calculations are extremely close, but not
exactly
• Unable to predict unknown compound types
• No guarantee to trust calculations
 Advantages
• Once atom has been parameterized, all
possible compounds can be calculated
• Ability to describe bond breaking and forming
reactions
• Provide methods for calculating electronic
wave functions
• Save on amount of time for calculations
 Summary
• Use of Semi-Empirical methods provides
relatively-reliable, time-efficient calculations
of chemical systems via minimal basis sets
• Several different methods have been
discussed:
– NDO’s, MINDO, AM1, PM3