Measuring correlated electron motion in atoms with the momentum-balance density.

Abstract

Three new measures of relative electron motion are introduced: equimomentum, antimomentum, and momentum-balance. The equimomentum is the probability that two electrons have the exact same momentum, whereas the antimomentum is the probability that their momenta are the exact opposite. Momentum-balance (MB) is the difference between the equimomentum and antimomentum and, therefore, indicates if equal or opposite momentum is more probable in a system of electrons. The equimomentum, antimomentum, and MB densities are also introduced, which are the local contribution to each quantity. The MB and MB density of the extrapolated-full configuration interaction wave functions of atoms of the first three rows of the periodic table are analyzed, with a particular focus on contrasting the correlated motion of electrons with opposite-spin and parallel-spin. Coulomb correlation between opposite-spin electrons leads to a higher probability of equimomentum, whereas Fermi correlation between parallel-spin electrons leads to a higher probability of antimomentum. The local contribution to MB, given an electron is present, is a minimum at the nucleus and generally increases as the distance from the nucleus increases. There are also interesting similarities between the effects of Fermi correlation and Coulomb correlation (of opposite-spin electrons) on MB.