Energy surface, chemical potentials, Kohn-Sham energies in spin-polarized density functional theory

TL;DR

This paper analyzes the energy surface and chemical potentials in spin-polarized density functional theory, linking derivatives of energy to ionization potentials, electron affinities, and Kohn-Sham orbital energies under magnetic fields.

Contribution

It provides a detailed analysis of the energy surface, derivatives, and Kohn-Sham energies in spin-polarized DFT, including cases with non-convex energy surfaces and external magnetic fields.

Findings

Derivatives of energy relate to ionization potentials and electron affinities.

Kohn-Sham orbital energies correspond to ionization potentials and affinities.

Discontinuities in derivatives are analyzed and connected to potential changes.

Abstract

On the basis of the zero-temperature grand canonical ensemble generalization of the energy E[N,N_s,v,B] for fractional particle N and spin N_s numbers, the energy surface over the (N,N_s) plane is displayed and analyzed in the case of homogeneous external magnetic fields B(r). The (negative of the) left/right-side derivatives of the energy with respect to N, N_up, and N_down give the fixed-N_s, spin-up, and spin-down ionization potentials/electron affinities, respectively, while the derivative of E[N,N_s,v,B] with respect to N_s gives the (signed) half excitation energy to a state with N_s increased (or decreased) by 2. The highest occupied and lowest unoccupied Kohn-Sham spin-orbital energies are identified as the corresponding spin-up and spin-down ionization potentials and electron affinities. The excitation energies to the states with N_s+2, N_s-2, can be obtained as the differences between the lowest unoccupied and the opposite-spin highest occupied spin-orbital energies, if the (N,N_s) representation of the Kohn-Sham spin-potentials is used. The cases where the convexity condition on the energy does not hold are also discussed. Finally, the discontinuities of the energy derivatives and the Kohn-Sham potential are analyzed and related.