Realistic quantitative descriptions of electron transfer reactions: diabatic free-energy surfaces from first-principles molecular dynamics.

  title={Realistic quantitative descriptions of electron transfer reactions: diabatic free-energy surfaces from first-principles molecular dynamics.},
  author={Patrick H.-L. Sit and Matteo Cococcioni and Nicola Marzari},
  journal={Physical review letters},
  volume={97 2},
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… Expand
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