Transition state barriers in multidimensional Marcus theory.
Multidimensional Marcus theory is the extension of traditional Marcus theory to systems in which multiple particles are transferred. Rather than the intersecting parabolas of Marcus theory, multidimensional Marcus theory involves the intersection of paraboloids. In this paper, we examine the conditions under which a full multidimensional treatment of these paraboloids is necessary and when it is possible to use a simpler one-dimensional formalism. In particular, we examine transition state barrier energies, which are essential parameters in many reaction rate equations, and which depend on the formalism used. We find, based on both analytic calculations and numerical simulation, that the reduced one-dimensional treatment yields excellent agreement with the exact, multidimensional results over a wide variety of conditions for one particular choice of the single collective reaction coordinate. We also outline a procedure for calculating accurate multidimensional transition state barrier energies and apply it to a two-dimensional model of proton-coupled electron transfer.
Zwickl
Jill
J
Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA.
Shenvi
Neil
N
Schmidt
J R
JR
Tully
John C
JC
D003198:Computer Simulation; D004583:Electrons; D008956:Models, Chemical; D011789:Quantum Theory; D012997:Solvents / Q000737:chemistry; D013816:Thermodynamics
D012997:Solvents