Quantum states of physical domains in molecular systems: A three-state model approach

Abstract

The physical regions (domains or basins) within the molecular structure are open systems that exchange charge between them and, consequently,house a fractional number of electrons (net charge). The natural framework describing the quantum states for these domains is thedensity matrix (DM) in its grand-canonical version, which corresponds to a convex expansion into a set of basis states of an integer numberof electrons. In this report, it is shown that the solution for these quantities is supported by the DM expansion into three states of differentnumbers of particles: the neutral and two (edge) ionic states. The states and the average number of particles in the domains (fractional occupationpopulation) are determined by the coefficients of the expansion in terms of the fundamental transference magnitudes, revealing thedonor/acceptor character of the domains by which the quantum accessible states are discussed.