TY - JOUR
T1 - Adiabatic elimination in multidimensional diffusive barrier crossing
AU - Rabinovich, Savely
AU - Agmon, Noam
PY - 1991/8/2
Y1 - 1991/8/2
N2 - We consider the (reaction-coordinate) viscosity dependence of reaction-rate coefficients for the two-dimensional Agmon-Kosloff surface. We show that rate coefficients calculated from the Agmon-Hopfield sink-Smoluchowski equation are a lower bound, approaching asymptotically the two-dimensional result for fast reactive-mode diffusion. A modified equation, employing an effective potential in the spirit of a recent suggestion by the Karpov group, yields a promising approximation over most of the viscosity range.
AB - We consider the (reaction-coordinate) viscosity dependence of reaction-rate coefficients for the two-dimensional Agmon-Kosloff surface. We show that rate coefficients calculated from the Agmon-Hopfield sink-Smoluchowski equation are a lower bound, approaching asymptotically the two-dimensional result for fast reactive-mode diffusion. A modified equation, employing an effective potential in the spirit of a recent suggestion by the Karpov group, yields a promising approximation over most of the viscosity range.
UR - http://www.scopus.com/inward/record.url?scp=33748508734&partnerID=8YFLogxK
U2 - 10.1016/0009-2614(91)80225-M
DO - 10.1016/0009-2614(91)80225-M
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AN - SCOPUS:33748508734
SN - 0009-2614
VL - 182
SP - 336
EP - 342
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 3-4
ER -