Kohn–Sham exchange-correlation potentials from second-order reduced density matrices

We describe a practical algorithm for constructing the Kohn–Sham exchange-correlation potential corresponding to a given second-order reduced density matrix. Unlike conventional Kohn–Sham inversion methods in which such potentials are extracted from ground-state electron densities, the proposed technique delivers unambiguous results in finite basis sets. The approach can also be used to separate approximately the exchange and correlation potentials for a many-electron system for which the reduced density matrix is known. The algorithm is implemented for configuration-interaction wave functions and its performance is illustrated with numerical examples.

Kohn–Sham exchange-correlation potentials from second-order reduced density matrices Journal Articles