Some simple explicit examples of correlated one‐electron theory and density matrix functionals

Abstract

AbstractSome examples are presented displaying how general spin orbitals (GSOs) and their occupation numbers uniquely determine N‐electron antisymmetrized geminal power states. This provides a correlated one‐electron model that generalizes the independent particle model that is universally used in picturing chemical behavior. These examples also demonstrate that one‐electron models, involving GSOs and occupation numbers, and the one based on a first order density matrix are not equivalent. This difference is shown by displaying sets of different GSOs that have the same occupation numbers that correspond to the same density matrix but different N‐electron states. This observation also leads to the explicit construction of a density matrix functional. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008