Inter-basin dynamics on multidimensional potential surfaces. I. Escape rates on complex basin surfaces

In this report, we present a general prescription for computing the escape rate of the system from a basin with full consideration of the topographica l fingerprint of that basin. The method is based on a solution of the reduc ed Fokker-Planck equation and built up to allow the separation of the inter -basin dynamics from that of the intra-basin motion. The main result is tha t when local well populations thermalize within a basin, local minima, espe cially those of higher energy, enhance the escape rate from the basin. Also , numerical analyses lead to the inference that kinetic traps of "wrong" st ructures are distinctive topographical patterns which may produce kinetic p roperties similar to those of the primary basin, i.e., that containing the global minimum, but lie in other basins. (C) 2001 American Institute of Phy sics.