PHYS 552 |
| Multidimensional Marcus theory, the extension of traditional Marcus theory to systems in which multiple particles are transferred, is the basis of theories of proton-coupled electron transfer in solutions. 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 they can be collapsed to a simpler one-dimensional formalism. 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 will also outline a procedure for calculating accurate multidimensional transition state barrier energies, applying it to a two-dimensional model problem involving proton-coupled electron transfer. |
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PHYS Poster Session - General Theory
7:30 PM-10:00 PM, Wednesday, April 9, 2008 Morial Convention Center -- Hall A, Poster
Division of Physical Chemistry |