Energy barrier scalings in driven systems.
Energy landscape mappings are performed for two different molecular systems under mechanical loads. Barrier heights are observed to scale as Delta U approximately delta(3/2), where delta is a residual load. Catastrophe theory predicts that this scaling should arise for vanishing delta; however, this region is irrelevant in physical processes at finite temperature because thermal fluctuations cause the system to cross over the barrier before reaching the small-delta regime. Surprisingly, we find that the Delta U approximately delta(3/2), scaling is valid far beyond the vanishing delta regime described by catastrophe theory. We discuss how this scaling will therefore be relevant at finite temperatures and gives corrections to Eyring's theory for transition rates.
Maloney
Craig E
CE
Department of Physics, University of California, Santa Barbara, California 93106, USA and Lawrence Livermore National Lab CMS/MSTD, Livermore, California 94550, USA.
Lacks
Daniel J
DJ