Electron group functions for the analysis of the electronic structures of molecules.
The electronic structure of a vast majority of molecular systems can be understood in terms of electron groups and their wave functions. They serve as a natural basis for bringing intuitive chemical and physical concepts into quantum chemical calculations. This article considers the general electron group functions formalism as well as its simple geminal version. We try to characterize the wave function with the group structure and its capabilities in actual calculations. For this purpose we implement a variational method based on the wave function in the form of an antisymmetrized product of strongly orthogonal group functions and perform a series of electronic structure calculations for small molecules and model systems. The most important point studied is the relation between the choice of electron groups and the results obtained. We consider energetic characteristics as well as optimal geometry parameters. In view of practical importance, the structure of variationally optimized local one-electron states is considered in detail as well as intuitive characteristics of chemical bonds.
Tokmachev
A M
AM
Institut für Anorganische Chemie, Rheinisch-Westfälische Technische Hochschule, Prof.-Pirlet-Str. 1, 52056 Aachen. andrei.tokmachev@ac.rwth-aachen.de
Dronskowski
R
R