6533b855fe1ef96bd12afefd

RESEARCH PRODUCT

The influence of the solvent's mass on the location of the dividing surface for a model Hamiltonian

Stephen WigginsBarry K. CarpenterRafael García-meseguer

subject

PhysicsDynamical systems theoryMathematical analysisSolvationlcsh:QD450-801General Physics and Astronomylcsh:Physical and theoretical chemistryDividing surfaceSurface reactionSistemes dinàmics diferenciablesChemical reactionlcsh:QC1-999Reactions in solutionSolventsymbols.namesakeReaction rate constantEffective mass (solid-state physics)Dynamical systemssymbolsPhysical and Theoretical ChemistryHamiltonian (quantum mechanics)lcsh:PhysicsFisicoquímica

description

The Transition State dividing surface is a key concept, not only for the precise calculation of the rate constant of a reaction, but also for the proper prediction of product ratios. The correct location of this surface is defined by the requirement that reactive trajectories do not recross it. In the case of reactions in solution the solvent plays an important role in the location of the dividing surface. In this paper we show with the aid of a model Hamiltonian that the effective mass of the solvent can dramatically change the location of the dividing surface. Keywords: Dynamical systems, Dividing surface, Reactions in solution, 2019 MSC: 00-01, 99-00

yearjournalcountryeditionlanguage
2019-07-01
10.1016/j.cpletx.2019.100030https://doi.org/10.1016/j.cpletx.2019.100030