ISSN:
0040-5744
Schlagwort(e):
Key words: Zero differential overlap
;
Semiempirical MO methods
;
Löwdin transformation
;
Overlap density
;
Mulliken approximation
Quelle:
Springer Online Journal Archives 1860-2000
Thema:
Chemie und Pharmazie
Notizen:
Summary. Some systematic errors of the zero differential overlap (ZDO) approximation in semiempirical molecular orbital (MO) methods are discussed. In π electron methods, a power series expansion of the inverse square root S -1/2 of the overlap matrix and application of the Mulliken approximation to the two-electron integrals show that the ZDO Hamiltonian coincides with the Hamiltonian obtained by explicit performance of the Löwdin transformation up to first-order terms of diatomic overlap densities. Higher than first-order terms lead to a systematic up-shift of the canonical MO energies. Although a power series expansion of S -1/2 is no longer possible in all-valence-electron methods, the MO levels resulting from the ZDO approximation are also systematically placed at too low energies, especially the low-lying occupied and the virtual MOs. A method based on explicit performance of the Löwdin transformation and retaining the simplicity of the ZDO approach for the calculation of Fock matrix elements is developed. The parameters of this method are obtained by very simple manipulations of the original ZDO parameters. Numerical calculations show that a considerable improvement of the MO energy spectrum in the inner valence region can be obtained in this way
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1007/BF01134202
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