Closed-form expression relating the second-order component of the density functional theory correlation energy to its functional derivative

Abstract

For helping to improve approximations to the density-functional exchange-correlation energy, Exc[n], and its functional derivative, the difference between the second-order component of the correlation energy, Ec(2)[n], and the integral ∫dr vc(2)([n];r)n(r), involving its functional derivative, vc(2)([n];r), is given in terms of only the occupied Kohn–Sham orbitals and the exchange potential. The quantity 2Ec(2)[n] is especially significant because it is the initial slope in the adiabatic connection formula for Exc[n]. The analytic expression for 2Ec(2)[n]−∫dr vc(2)([n];r)n(r) is obtained for any spherically symmetric two-electron test density. Numerical examples are presented.