Determination of energies and electronic densities of functional groups according to partitionings in the physical space

Abstract

This work formulates our previously reported partitionings of the first-order reduced density matrix and the molecular electronic energy using for both quantities an identical mathematical framework. The procedure provides a consistent and rigorous scheme for extending our algorithms to unions of atomic domains, in order to describe molecular fragments which can be identified as functional groups. Numerical determinations, performed in several series of organic compounds and clusters, support the reliability of our methodology to describe properties of atomic groups. © 2008 American Chemical Society.