The Pauli principle and the confinement of electron pairs in a double well: Aspects of electronic bonding under pressure.

Abstract

It has become recently clear that chemical bonding under pressure is still lacking guiding principles for understanding the way electrons reorganize when their volume is constrained. As an example, it has recently been shown that simple metals can become insulators (aka electrides) when submitted to high enough pressures. This has lead to the general believe that "a fundamental yet empirically useful understanding of how pressure alters the chemistry of the elements is lacking" [R. J. Hemley, High Pressure Res. 30, 581 (2010)]. In this paper, we are interested in studying the role that the Pauli principle plays on the localization/delocalization of confined noninteracting electrons. To this end, we have considered the simple case of a 1-dimensional (1-D) double well as a confining potential, and the Electron Localization Function (ELF) has been used to characterize the degree localization/delocalization of the systems of noninteracting electrons. Then, we have systematically studied the topology of the ELF as a function of the double well parameters (barrier eight and wells distance) and of the number of electrons. We have found that the evolution of the ELF distributions has a good correspondence with the evolution of chemical bonding of atomic solids under pressure.