Evaluation of 〈<i>S</i>2〉 in restricted, unrestricted Hartree–Fock, and density functional based theories

Abstract

A simple formalism for the evaluation of 〈S2〉 in terms of the two-particle density matrix is presented. The implementation of the formalism in the restricted open-shell Hartree–Fock (ROHF), unrestricted HF (UHF) and density functional (DFT) based theories is discussed. Rules governing the nonzero S2 matrix elements in the UHF based methods are presented. Further examples are given of 〈S2〉 in several atomic and radical systems from very simple density functional models.