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Charge constrained density functional molecular dynamics for simulation of condensed phase electron transfer reactions

J. Chem. Phys. 131, 064101 (2009); doi:10.1063/1.3190169

Published 10 August 2009

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Harald Oberhofer and Jochen Blumberger
Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom
We present a plane-wave basis set implementation of charge constrained density functional molecular dynamics (CDFT-MD) for simulation of electron transfer reactions in condensed phase systems. Following the earlier work of Wu and Van Voorhis [Phys. Rev. A 72, 024502 (2005)], the density functional is minimized under the constraint that the charge difference between donor and acceptor is equal to a given value. The classical ion dynamics is propagated on the Born–Oppenheimer surface of the charge constrained state. We investigate the dependence of the constrained energy and of the energy gap on the definition of the charge and present expressions for the constraint forces. The method is applied to the Ru2+–Ru3+ electron self-exchange reaction in aqueous solution. Sampling the vertical energy gap along CDFT-MD trajectories and correcting for finite size effects, a reorganization free energy of 1.6 eV is obtained. This is 0.1−0.2 eV lower than a previous estimate based on a continuum model for solvation. The smaller value for the reorganization free energy can be explained by the fact that the Ru–O distances of the divalent and trivalent Ru hexahydrates are predicted to be more similar in the electron transfer complex than for the separated aqua ions. ©2009 American Institute of Physics
History: Received 28 April 2009; accepted 8 July 2009; published 10 August 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/064101/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.20.Wt
    Computational modeling and simulation of chemical kinetics
  • 82.30.Fi
    Ion-molecule, ion-ion, and charge-transfer chemical reactions
  • 82.30.Hk
    Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)
  • YEAR: 2009

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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