Generalizing the Marcus equation
William W. Parson
Abstract
The Marcus equation for the rate of an electron-transfer reaction can be generalized to cover larger electronic-interaction matrix elements, irregular free-energy surfaces, and coupling to multiple vibrational modes and to recognize the different effects of vibrational relaxations and pure dephasing. Almost all the information needed to calculate the rate constant can be obtained from a quantum-classical molecular dynamics simulation of the system in the reactant state. Because the final expression for the rate constant does not depend on the reorganization energy, it is insensitive to slow relaxations that follow the reaction.
Topics & Concepts
DephasingMarcus theoryReaction rate constantConstant (computer programming)Master equationChemistryElectron transferMatrix (chemical analysis)Cover (algebra)Molecular dynamicsQuantumCoupling constantCoupling (piping)Quantum mechanicsStatistical physicsPhysicsThermodynamicsComputational chemistryPhysical chemistryMaterials scienceKineticsComputer scienceProgramming languageChromatographyMechanical engineeringMetallurgyEngineeringMolecular Junctions and NanostructuresPhotochemistry and Electron Transfer StudiesSpectroscopy and Quantum Chemical Studies