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A fresh look at ensembles: Derivative discontinuities in density functional theory

Chan, Garnet Kin-Lic (1999) A fresh look at ensembles: Derivative discontinuities in density functional theory. Journal of Chemical Physics, 110 (10). pp. 4710-4723. ISSN 0021-9606. doi:10.1063/1.478357.

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We present a zero temperature ensemble spin density functional theory. We discuss the ensemble quantities that arise from derivative discontinuities, including the nonvanishing asymptotic potential and band gap shift, in the context of the Kohn–Sham formalism, and hybrid exact exchange theories, such as the Hartree–Fock–Kohn–Sham formalism. We describe and implement a general method of calculating these quantities in atomic and molecular systems. Finally we discuss how our results explain the deficiencies of existing functionals, and how new functionals should be constructed, illustrating our conclusions by examining the dissociation of H^(+)_2.

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Chan, Garnet Kin-Lic0000-0001-8009-6038
Additional Information:© 1999 American Institute of Physics. Received 04 September 1997. Accepted 10 November 1998.
Issue or Number:10
Record Number:CaltechAUTHORS:20160715-151036445
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:69068
Deposited By: Donna Wrublewski
Deposited On:20 Jul 2016 23:26
Last Modified:11 Nov 2021 04:08

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