Domain-averaged Fermi hole and Domain-restricted reduced density matrices: a critical comparison

D. R. ALCOBA, R. C. BOCHICCHIO, L. LAIN, A. TORRE

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

JOHN WILEY & SONS INC

Año: 2011 vol. 111 p. 256 - 262

0020-7608

The knowledge of the properties and the applicability of domain-restricted matrices has provided important advances in the description of molecular electronic distributions. In this work, we perform a critical comparison between two different methods: the domain-averaged Fermi hole (DAFH) approach and the domain-restricted first-order reduced density matrix (DRRDM) one, focusing our study on both physical and mathematical points of view. Our results permit to show that bothmethods have a markedly different behavior at correlated wave function level: the DAFHapproach provides information related with electron cloud localization and populationswhile the DRRDM is a true density matrix. To exemplify the theoretical discussion, wepresent a numerical test example and a simple analytical model that show such feature