Electron Transfer Rates in Polar and Non-Polar Environments: a Generalization of Marcus’ Theory to Include an Effective Treatment of Tunneling Effects
Anna Leo, Andrea Peluso
Abstract
A multistep kinetic model in which solvent motion is treated in the framework of Marcus theory and the rates of the elementary electron transfer step are evaluated at full quantum mechanical level is proposed and applied to the calculation of the rates of intramolecular electron transfer reactions in rigidly spaced D-Br-A (D = 1,1'-biphenyl radical anion, Br = androstane) compounds, for five acceptors (A) in three organic solvents with different polarity. The calculated rates agree well with experimental ones, and their temperature dependence is almost quantitatively reproduced.
Topics & Concepts
Marcus theoryElectron transferIntramolecular forceChemistryPolarQuantum tunnellingQuantumGeneralizationTransfer (computing)IonChemical physicsComputational chemistryPolarity (international relations)ElectronAdsorptionAtomic physicsThermodynamicsPhysical chemistryQuantum mechanicsPhysicsReaction rate constantKineticsStereochemistryOrganic chemistryMathematicsBiochemistryParallel computingCellComputer scienceMathematical analysisPhotochemistry and Electron Transfer StudiesFree Radicals and AntioxidantsAdvanced Chemical Physics Studies