Levy Constrained Search in Fock Space: An Alternative Approach to Noninteger Electron Number

doi:10.3866/PKU.WHXB201711071

Abstract

Abstract:

By extending the Levy wavefunction constrained search to Fock Space, one can define a wavefunction constrained search for electron densities in systems having noninteger number of electrons. For pure-state v-representable densities, the results are equivalent to what one would obtain with the zero-temperature grand canonical ensemble. In other cases, the wavefunction constrained search in Fock space presents an upper bound to the grand canonical ensemble functional. One advantage of the Fock-space wavefunction constrained search functional over the zero-temperature grand-canonical ensemble constrained search functional is that certain specific excited states (i.e., those that are not ground-state v-representable) are the stationary points of the Fock-space functional. However, a potential disadvantage of the Fock-space constrained search functional is that it is not convex.

Key words: Density functional theory, Levy constrained search functional, Fock space, Fractional electron number, Excited-state density functional theory, Universal density functional, Zero temperature grand canonical ensemble, Convexity

Paul W. AYERS,Mel LEVY. Levy Constrained Search in Fock Space: An Alternative Approach to Noninteger Electron Number[J]. Acta Phys. -Chim. Sin. 2018, 34(6), 625-630. doi: 10.3866/PKU.WHXB201711071

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