A study of the partitioning of the first-order reduced density matrix according to the theory of atoms in molecules

Diego R Alcoba; Luis Lain; Alicia Torre; Roberto C Bochicchio

doi:10.1063/1.2069927

A study of the partitioning of the first-order reduced density matrix according to the theory of atoms in molecules

J Chem Phys. 2005 Oct 8;123(14):144113. doi: 10.1063/1.2069927.

Authors

Diego R Alcoba¹, Luis Lain, Alicia Torre, Roberto C Bochicchio

Affiliation

¹ Departamento de Química Física, Facultad de Ciencias, Universidad del País Vasco, Bilbao, Spain.

PMID: 16238380
DOI: 10.1063/1.2069927

Abstract

This work describes a simple spatial decomposition of the first-order reduced density matrix corresponding to an N-electron system into first-order density matrices, each of them associated to an atomic domain defined in the theory of atoms in molecules. A study of the representability of the density matrices arisen from this decomposition is reported and analyzed. An appropriate treatment of the eigenvectors of the matrices defined over atomic domains or over unions of these domains allows one to describe satisfactorily molecular properties and chemical bondings within a determined molecule and among its fragments. Numerical determinations, performed in selected molecules, confirm the reliability of our proposal.