Use of Harriman’s construction in determining molecular equilibrium states

Abstract

Information-theoretic description of the electron probabilities and currents in molecules is extended to cover the complex amplitudes (wave functions) of quantum mechanics. The classical information measures of Fisher and Shannon, due to the probability/density distributions themselves, are supplemented by the nonclassical terms generated by the wave-function phase or the associated probability current. The previous one-electron development in such an entropic perspective on the molecular electronic structure is extended to cover N-electron states by adopting the Harriman-type framework of equidensity orbitals. This analysis emphasizes the phase part of electronic states, which generates the probability-current density and the associated non-classical entropy contributions, which allow one to distinguish the information content of states generating the same electron density and differing in their current composition. A complementary character of the Fisher and Shannon information measures is explored in the associated vertical (density-constrained) information principles, for determining the equilibrium state corresponding to the fixed ground-state electron density. It is argued that the lowest “thermodynamic” state generally differs from the true ground state of the system, by exhibiting the space-dependent phase and hence also the non-vanishing probability current, linked to the system electron distribution.