1-Matrix functional for long-range interaction energy of two hydrogen atoms

Abstract

The leading terms in the large-R asymptotics of the functional of the one-electron reduced density matrix for the ground-state energy of the H2 molecule with the internuclear separation R are derived thanks to the solution of the phase dilemma at the R → ∞ limit. At this limit, the respective natural orbitals (NOs) are given by symmetric and antisymmetric combinations of “half-space” orbitals with the corresponding natural amplitudes having the same amplitudes but opposite signs. Minimization of the resulting explicit functional yields the large-R asymptotics for the occupation numbers of the weakly occupied NOs and the C6 dispersion coefficient. The highly accurate approximates for the radial components of the p-type “half-space” orbitals and the corresponding occupation numbers (that decay like R−6), which are available for the first time thanks to the development of the present formalism, have some unexpected properties.