Molecular dynamics simulation of proton-coupled electron transfer in solution

Mark N. Kobrak, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

18 Scopus citations


A new approach for the molecular dynamics simulation of proton-coupled electron transfer reactions in solution is presented. The solute is represented by a four-state valence bond model, and the solvent is described by explicit solvent molecules. The nuclear quantum effects of the transferring hydrogen are incorporated with a procedure based on a series of purely classical molecular dynamics simulations. The resulting mixed electronic/vibrational free energy surfaces depend on two solvent reaction coordinates corresponding to electron and proton transfer. This approach is shown to be equivalent to adiabatic mixed quantum/classical molecular dynamics, in which the nuclear quantum effects are included during the simulation, under well-defined, physically reasonable conditions. The results of the application of this approach to a model system are compared to those from a previous study based on a dielectric continuum treatment of the solvent. In addition, specific molecular motions of the solvent associated with proton-coupled electron transfer are identified, and solvent configurations that couple the proton and electron transfer reactions are characterized. This methodology may be implemented using commercial molecular dynamics software packages with little or no modification to the existing programs.

Original languageEnglish (US)
Pages (from-to)10435-10445
Number of pages11
JournalJournal of Physical Chemistry B
Issue number42
StatePublished - Oct 25 2001
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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