Orbital-free quantum crystallography: view on forces in crystals

Abstract

Quantum theory of atoms in molecules and the orbital-free density functional theory (DFT) are combined in this work to study the spatial distribution of electrostatic and quantum electronic forces acting in stable crystals. The electron distribution is determined by electrostatic electron mutual repulsion corrected for exchange and correlation, their attraction to nuclei and by electron kinetic energy. The latter defines the spread of permissible variations in the electron momentum resulting from the de Broglie relationship and uncertainty principle, as far as the limitations of Pauli principle and the presence of atomic nuclei and other electrons allow. All forces are expressed via kinetic and DFT potentials and then defined in terms of the experimental electron density and its derivatives; hence, this approach may be considered as orbital-free quantum crystallography. The net force acting on an electron in a crystal at equilibrium is zero everywhere, presenting a balance of the kinetic F kin( r ) and potential forces F ( r ). The critical points of both potentials are analyzed and they are recognized as the points at which forces F kin( r ) and F ( r ) individually are zero (the Lagrange points). The positions of these points in a crystal are described according to Wyckoff notations, while their types depend on the considered scalar field. It was found that F ( r ) force pushes electrons to the atomic nuclei, while the kinetic force F kin( r ) draws electrons from nuclei. This favors formation of electron concentration bridges between some of the nearest atoms. However, in a crystal at equilibrium, only kinetic potential v kin( r ) and corresponding force exhibit the electronic shells and atomic-like zero-flux basins around the nuclear attractors. The force-field approach and quantum topological theory of atoms in molecules are compared and their distinctions are clarified.