When Density Functional Theory goes wrong and how to fix it: spin balanced unrestricted Kohn-Sham formalism

Abstract

Kohn-Sham (KS) formalism of Density Functional Theory is modified to include the systems with strong non-dynamic electron correlation. Unlike in extended KS and broken symmetry unrestricted KS formalisms, cases of both singlet-triplet and aufbau instabilities are covered, while preserving a pure spin-state. The straightforward implementation is suggested, which consists of placing spin constraints on complex unrestricted Hartree-Fock wave function. Alternative approximate approach consists of using the perfect pairing implementation with the natural orbitals of unrestricted KS method and square roots of their occupation numbers as configuration weights without optimization, followed by a posteriori exchange-correlation correction. The numerical results of this approximation for the barrier to the internal rotation in ethylene are reported to be in close agreement with experimental data.