Physics – Condensed Matter – Materials Science
Scientific paper
2006-06-13
Physics
Condensed Matter
Materials Science
5 pages, 4 figures, accepted for publication in Phys. Rev. Lett
Scientific paper
10.1103/PhysRevLett.97.028303
A general approach to calculate the diabatic surfaces for electron-transfer reactions is presented, based on first-principles molecular dynamics of the active centers and their surrounding medium. The excitation energy corresponding to the transfer of an electron at any given ionic configuration (the Marcus energy gap) is accurately assessed within ground-state density-functional theory via a novel penalty functional for oxidation-reduction reactions that appropriately acts on the electronic degrees of freedom alone. The self-interaction error intrinsic to common exchange-correlation functionals is also corrected by the same penalty functional. The diabatic free-energy surfaces are then constructed from umbrella sampling on large ensembles of configurations. As a paradigmatic case study, the self-exchange reaction between ferrous and ferric ions in water is studied in detail.
Cococcioni Matteo
Marzari Nicola
Sit Patrick H. -L.
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