Semi-empirical quantum chemistry method

Semi-empirical quantum chemistry methods are based on the Hartree–Fock formalism, but make many approximations and obtain some parameters from empirical data. They are very important in computational chemistry for treating large molecules where the full Hartree–Fock method without the approximations is too expensive. The use of empirical parameters appears to allow some inclusion of electron correlation effects into the methods.

Within the framework of Hartree–Fock calculations, some pieces of information (such as two-electron integrals) are sometimes approximated or completely omitted. In order to correct for this loss, semi-empirical methods are parametrized, that is their results are fitted by a set of parameters, normally in such a way as to produce results that best agree with experimental data, but sometimes to agree with ab initio results.

Semi-empirical methods follow what are often called empirical methods where the two-electron part of the Hamiltonian is not explicitly included. For π-electron systems, this was the Hückel method proposed by Erich Hückel.^[1][2][3] For all valence electron systems, the extended Hückel method was proposed by Roald Hoffmann.^[4]

Semi-empirical calculations are much faster than their ab initio counterparts. Their results, however, can be very wrong if the molecule being computed is not similar enough to the molecules in the database used to parametrize the method.

Semi-empirical calculations have been most successful in the description of organic chemistry, where only a few elements are used extensively and molecules are of moderate size. However, semi-empirical methods were also applied to solids^[5] and nanostructures^[6] but with different parameterization.

As with empirical methods, we can distinguish methods that are:

• restricted to π-electrons. These method exist for the calculation of electronically excited states of polyenes, both cyclic and linear. These methods, such as the Pariser–Parr–Pople method (PPP), can provide good estimates of the π-electronic excited states, when parameterized well.^[7][8] Indeed, for many years, the PPP method outperformed ab initio excited state calculations.

or those:

• restricted to all valence electrons. These methods can be grouped into several groups:

• Methods such as CNDO/2, INDO and NDDO that were introduced by John Pople.^[9][10][11] The implementations aimed to fit, not experiment, but ab initio minimum basis set results. These methods are now rarely used but the methodology is often the basis of later methods.

• Methods that are in the MOPAC, AMPAC, and/or SPARTAN computer programs originally from the group of Michael Dewar.^[12] These are MINDO, MNDO,^[13] AM1,^[14] PM3,^[15] RM1[16] , PM6^[17] and SAM1. Here the objective is to use parameters to fit experimental heats of formation, dipole moments, ionization potentials, and geometries.

• Methods whose primary aim is to predict the geometries of coordination compounds, such as Sparkle/AM1, available for lanthanide complexes.

• Methods whose primary aim is to calculate excited states and hence predict electronic spectra. These include ZINDO and SINDO.^[18][19]

the latter being by far the largest group of methods.

The table below shows some software packages that carry out semi-empirical methods, indicating the other methods that they include where applicable.

Package	Molecular mechanics	Hartree–Fock	Post-Hartree–Fock methods	Density functional theory
AMPAC	N	N	N	N
CP2K	Y	Y	N	Y
GAMESS (UK)	N	Y	Y	Y
GAMESS (US)	N	Y	Y	Y
GAUSSIAN	Y	Y	Y	Y
MOLCAS	Y	Y	Y	Y
MOPAC	N	N	N	N
PC GAMESS	Y	Y	Y	Y
PQS	Y	Y	Y	Y
SPARTAN	Y	Y	Y	Y
SPARTAN Student	Y	Y	Y	Y
VASP	N	Y	Y	Y

See also

• Quantum chemistry computer programs

References