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Acta Phys. -Chim. Sin.
Special Issue: Special issue for Chemical Concepts from Density Functional Theory
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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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 wordsDensity 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: 25 September 2017      Published: 07 November 2017
Corresponding Authors: AYERS Paul W., LEVY Mel     E-mail: 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. Acta Phys. -Chim. Sin., 0, (): 0-0.

URL:

http://www.whxb.pku.edu.cn/10.3866/PKU.WHXB201711071     OR     http://www.whxb.pku.edu.cn/Y0/V/I/0

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