Correlated one-electron wave functions

摘要

A one-electron theory of many-electron systems that explicitly describes electron-electron correlation may be based on the observation that antisymmetrized geminal power (AGP) states are completely characterized by the occupation numbers of their first-order reduced density operators (FORDO) and a set of canonical general spin-orbitals (CGSOs), which are in general distinct from the natural general spin-orbitals. Because the FORDO alone does not determine an AGP state, a density matrix functional may be defined. A generalization of the independent-particle Fock operator serves to express the total state energy in terms of ionization energies, kinetic energies, and potential energies of the CGSOs. A one-electron picture of chemical bonding emerges from this theory. (c) 2005 Wiley Periodicals, Inc.