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ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 0,Vol.>> Issue()>> 0-0     doi: 10.3866/PKU.WHXB201711071         中文摘要
Accepted manuscript
Levy Constrained Search in Fock Space:An Alternative Approach to Noninteger Electron Number
AYERS Paul W.1, LEVY Mel2,3,4
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
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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.



Keywords: 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  
Received: 2017-09-25 Accepted: 2017-11-02 Publication Date (Web): 2017-11-07
Corresponding Authors: AYERS Paul W., LEVY Mel Email: ayers@mcmaster.ca;mlevy@tulane.edu


Cite this article: AYERS Paul W., LEVY Mel. Levy Constrained Search in Fock Space:An Alternative Approach to Noninteger Electron Number[J]. Acta Phys. -Chim. Sin., 0, (): 0-0.    doi: 10.3866/PKU.WHXB201711071

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