Interplayoftheoryandcomputationsin scienceExamplesdrawnfromtheoretical/experimentalstudiesofReactionratesOn-watercatalysiorganicreactionsIsotopefractionationSingle-moleculefluctuationsRudolphMarcusCalifornia Institute of TechnologyKITPC Workshop on Dynamics ofBiomolecular MachineryBeijing August 6, 2009
Interplay of theory and computations in science - Examples drawn from theoretical/experimental studies of Reaction rates On-water catalysiorganic reactions Isotope fractionation Single-molecule fluctuations Rudolph Marcus California Institute of Technology KITPC Workshop on Dynamics of Biomolecular Machinery Beijing August 6, 2009
ELECTRONTRANSFERREACTIONSISOTOPICEXCHANGE*2+Fe2+ + Fe*3+ → Fe3+ + FeK11*3+*4+→Ce4+Ce3++Ce*4+++CeK22CROSS-REACTIONSFe?+ + Ce4+ → Fe3+ + Ce3+K10
ElectronTransferFe3+(ag)+Fe2+Fe2+(ag)+Fe3+(aq)(aq)XN4VVVYAReactionCoordinate
ELECTRONTRANSEERMECHANISMReactantsProductsAGoReactionCoordinate
ELECTRON TRANSFER MECHANISM Reaction Coordinate Free Energy
Rate Constant for Electron Transfer△G)221+24 RTk= Ae
k = Ae − 4RT 1+ G 2 Rate Constant for Electron Transfer