The empirical valence bond (EVB) method [J. Chem. Phys. 52, 1262 (1970)] has always embodied charge transfer processes. The mechanism of that behavior is examined here and recast for use as a new empirical potential energy surface for large-scale simulations. A two-state model is explored. The main features of the model are: (1) explicit decomposition of the total system electron density is invoked; (2) the charge is defined through the density decomposition into constituent contributions; (3) the charge transfer behavior is controlled through the resonance energy matrix elements which cannot be ignored; and (4) a reference-state approach, similar in spirit to the EVB method, is used to define the resonance state energy contributions in terms of “knowable” quantities. With equal validity, the new potential energy can be expressed as a nonthermal ensemble average with a nonlinear but analytical charge dependence in the occupation number. Dissociation to neutral species for a gas-phase process is preserved. A variant of constrained search density functional theory is advocated as the preferred way to define an energy for a given charge.
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22 April 2004
Research Article|
April 05 2004
An empirical charge transfer potential with correct dissociation limits
Steven M. Valone;
Steven M. Valone
Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
Department of Physics and Astronomy, University of New Mexico, Albuquerque, New Mexico 87131
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Susan R. Atlas
Susan R. Atlas
Center for Advanced Studies and Department of Physics and Astronomy, University of New Mexico, Albuquerque, New Mexico 87131
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J. Chem. Phys. 120, 7262–7273 (2004)
Article history
Received:
November 14 2003
Accepted:
January 23 2004
Citation
Steven M. Valone, Susan R. Atlas; An empirical charge transfer potential with correct dissociation limits. J. Chem. Phys. 22 April 2004; 120 (16): 7262–7273. https://doi.org/10.1063/1.1676118
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