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Author Dale, Stephen G. ♦ Johnson, Erin R.
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ CORRECTIONS ♦ DENSITY FUNCTIONAL METHOD ♦ DNA ♦ POLARIZATION ♦ QUANTUM MECHANICS ♦ SELF-CONSISTENT FIELD ♦ SOLUTIONS ♦ SOLVATED ELECTRONS ♦ SOLVENTS ♦ TRAPPING
Abstract Exploration of the solvated electron phenomena using density-functional theory (DFT) generally results in prediction of a localised electron within an induced solvent cavity. However, it is well known that DFT favours highly delocalised charges, rendering the localisation of a solvated electron unexpected. We explore the origins of this counterintuitive behaviour using a model Kevan-structure system. When a polarisable-continuum solvent model is included, it forces electron localisation by introducing a strong energetic bias that favours integer charges. This results in the formation of a large energetic barrier for charge-hopping and can cause the self-consistent field to become trapped in local minima thus converging to stable solutions that are higher in energy than the ground electronic state. Finally, since the bias towards integer charges is caused by the polarisable continuum, these findings will also apply to other classical polarisation corrections, as in combined quantum mechanics and molecular mechanics (QM/MM) methods. The implications for systems beyond the solvated electron, including cationic DNA bases, are discussed.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2015-11-14
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 143
Issue Number 18


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