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Concept
Méthode quantique semi-empirique
Résumé
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. For all valence electron systems, the extended Hückel method was proposed by Roald Hoffmann.
Semi-empirical calculations are much faster than their ab initio counterparts, mostly due to the use of the zero differential overlap approximation. 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.
These methods 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. For many years, the PPP method outperformed ab initio excited state calculations.
These methods can be grouped into several groups:
Methods such as CNDO/2, INDO and NDDO that were introduced by John Pople. The implementations aimed to fit, not experiment, but ab initio minimum basis set results.
Source officielle
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