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Physical Review A

Energy components in spin-density functional theory

Federico E. Zahariev, Mark S. Gordon, Mel Levy

Published Aug 16, 2021• 2 citations
Publisher

Abstract

It has recently been shown how to replace spin-wave functions with purely spatial wave functions in the formulation of spin-density functional theory (SDFT), without any change to the resultant density functional expressions [F. Zahariev and M. Levy, Phys. Rev. A 100, 062507 (2019)]. The purely spatial wave functions that are obtained are much more convenient to use and thus allow for a relatively easy decomposition and manipulation of terms in the constrained-search formulation of SDFT. All the essential ingredients of SDFT, including the kinetic, exchange, and correlation contributions, are explicitly defined in terms of the universal functional expressed in this spin-free manner. Constrained-search derivations of the Oliver-Perdew relations for the kinetic and exchange terms are presented. The up-down spin component of the correlation term is found to contain the up-down spin component of the Hartree term. A spin-dependent generalization of the adiabatic connection is put forth and a connection with spin-dependent coordinate scaling is established for the correlation energy.

DOI
10.1103/physreva.104.022815

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It has recently been shown how to replace spin-wave functions with purely spatial wave functions in the formulation of spin-density functional theory (SDFT), without any change to the resultant density functional expressions [F. Zahariev and M. Levy, Phys. Rev. A 100, 062507 (2019)]. The purely spatial wave functions that are obtained are much more convenient to use and thus allow for a relatively easy decomposition and manipulation of terms in the constrained-search formulation of SDFT. All the essential ingredients of SDFT, including the kinetic, exchange, and correlation contributions, are explicitly defined in terms of the universal functional expressed in this spin-free manner. Constrained-search derivations of the Oliver-Perdew relations for the kinetic and exchange terms are presented. The up-down spin component of the correlation term is found to contain the up-down spin component of the Hartree term. A spin-dependent generalization of the adiabatic connection is put forth and a connection with spin-dependent coordinate scaling is established for the correlation energy.
Recently, nonuniqueness of external electrostatic and magnetic fields yielding a given many-electron ground state has been pointed out [K. Capelle and G. Vignale, Phys. Rev. Lett. 86, 5546 (2001); H. Eschrig and W. E. Pickett, Solid State Commun. 118, 123 (2001)], implying the nondifferentiability of the ground-state energy functional of spin-density-functional theory (SDFT), on the basis of which the applicability of widely used DFT methods in SDFT has been put into question and the need for a critical reexamination of those applications has been concluded. Here it is shown, for collinear magnetic fields, that the nonuniqueness of the external potentials in SDFT does not imply the nonexistence of number-conserving functional derivatives as well, with the use of which therefore problems arising from the nondifferentiability are avoided.
It is proven that entirely spin-free wave functions can be utilized in the basic definitions of the universal functionals in density-functional theory and spin-density-functional theory. Then, for the purpose of approximating these functionals, it is shown that the knowledge of certain properties of the functionals, such as those involving the coordinate scaling of just one of the spin densities, is made feasible precisely because the wave functions in the functional definitions are free of explicit spins. Among the examples, a conjectured spin-density scaling relation for the correlation energy is studied.
Many-electron theory is treated here with much attention focused on the synthesis of the density functional and density matrix theory. This synthesis shows that the exchange–correlation potential, normally obtained as the functional derivative with respect to the electron density of an assumed approximate exchange–correlation energy, can be written exactly in terms of the “near-diagonal” behavior of the fully interacting first-order density matrix and the diagonal of the second-order density matrix, thereby bypassing the functional derivative. Also involved, since the exchange–correlation potential is an “artifact” of reducing the many-electron Schrödinger equation to one-body Slater–Kohn–Sham equations, are the one-body orbitals derived from these latter equations, not just the density thereby obtained. This situation has then motivated a discussion of what constraints are placed on the low-order density matrices of atoms and molecules, described by an assumed spin-independent Hamiltonian, by the requirement that these matrices are constructed from an N-electron wave function which is an eigenfunction of the spin operators S2 and Sz. Some briefer discussion is added on the optimally convergent determinantal expansion of such an N-electron wave function, the relation between Brueckner and Löwdin natural orbitals being commented on as a by-product. In this latter context, it is noted that the exchange-only potential of density functional theory can be represented as a sum of two line integrals, each of which is path-dependent, the sum being, of course, path-independent. But in addition to knowledge of Slater–Kohn–Sham orbitals appearing as in the Harbola–Sahni exchange-only potential (which is one of the path-dependent terms), there is a kinetic correction. This involves Löwdin natural orbitals and their occupation numbers, but only now in the weak coupling limit of the electron–electron interaction, as emphasized in the kinetic “correction” to the Harbola–Sahni formula exhibited by Levy and the writer. Some directions for further work are briefly set out. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 74: 163–176, 1999
Within density functional theory, a coordinate-scaling relation for the coupling-constant dependence of the exchange-correlation kernel ${f}_{\mathrm{xc}}(\mathbf{r},{\mathbf{r}}^{\ensuremath{'}};\ensuremath{\omega})$ is utilized to express the correlation energy of a many-electron system in terms of fxc.{f}_{\mathrm{xc}}.fxc​. As a test of several of the available approximations for the exchange-correlation kernel, or equivalently the local-field factor, we calculate the uniform-gas correlation energy. While the random phase approximation (fxc{(f}_{\mathrm{xc}}(fxc​ === 0) makes the correlation energy per electron too negative by about 0.5 eV, the adiabatic local-density approximation [fxc[{f}_{\mathrm{xc}}[fxc​ === fxc(q{f}_{\mathrm{xc}}(qfxc​(q === $0,\ensuremath{\omega}$ === 0)] makes a comparable error in the opposite direction. The adiabatic nonlocal approximation [fxc[{f}_{\mathrm{xc}}[fxc​ === ${f}_{\mathrm{xc}}(q,\ensuremath{\omega}$ === 0)] reduces this error to about 0.1 eV, and inclusion of the full frequency dependence [fxc[{f}_{\mathrm{xc}}[fxc​ === ${f}_{\mathrm{xc}}(q,\ensuremath{\omega})]$ in an approximate parametrization reduces it further to less than 0.02 eV. We also report the wave-vector analysis and the imaginary-frequency analysis of the correlation energy for each choice of kernel.
Abstract Exact equations for correlation energy and kinetic energy correction functionals are derived in the time‐dependent density functional theory. Hierarchies of equations are also obtained and approximate functionals are proposed by truncation of the hierarchies at different orders. Explicit relations for the correlation energy and its kinetic component along the adiabatic path are given in terms of powers of the moments of the electron density. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003