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

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

AYERS Paul W. ^1,, ,
LEVY Mel ^2,3,4,,

1.
Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario L8S 4M1, Canada
2.
Department of Physics, North Carolina A & T State University, Greensboro, NC 27411, USA
3.
Department of Chemistry, Duke University, Durham, NC 27708, USA
4.
Department of Chemistry, Tulane University, New Orleans, LA 70118, USA

Corresponding author: AYERS Paul W., ayers@mcmaster.ca LEVY Mel, mlevy@tulane.edu
Received Date: 25 September 2017
Revised Date: 2 November 2017
Accepted Date: 2 November 2017
Available Online: 7 June 2017

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.
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