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Volume 195, 2016
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Kramers' theory for diffusion on a periodic potential

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Abstract

Kramers' turnover theory, based on the dynamics of the collective unstable normal mode (also known as PGH theory), is extended to the motion of a particle on a periodic potential interacting bilinearly with a dissipative harmonic bath. This is achieved by considering the small parameter of the problem to be the deviation of the collective bath mode from its value along the reaction coordinate, defined by the unstable normal mode. With this change, the effective potential along the unstable normal mode remains periodic, albeit with a renormalized mass, or equivalently a renormalized lattice length. Using second order classical perturbation theory, this not only enables the derivation of the hopping rates and the diffusion coefficient, but also the derivation of finite barrier corrections to the theory. The analytical results are tested against numerical simulation data for a simple cosine potential, ohmic friction, and different reduced barrier heights.

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Submitted
02 May 2016
Accepted
31 May 2016
First published
02 Jun 2016

Faraday Discuss., 2016,195, 111-138
Article type
Paper

Kramers' theory for diffusion on a periodic potential

R. Ianconescu and E. Pollak, Faraday Discuss., 2016, 195, 111
DOI: 10.1039/C6FD00105J

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