期刊
JOURNAL OF CHEMICAL PHYSICS
卷 140, 期 10, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/1.4867500
关键词
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资金
- Robert A. Welch Foundation [F-1514]
- National Science Foundation [CHE 1266380]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1266380] Funding Source: National Science Foundation
We propose a method for computing the activation barrier for chemical reactions involving molecules subjected to mechanical stress. The method avoids reactant and transition-state saddle optimizations at every force by, instead, solving the differential equations governing the force dependence of the critical points (i.e., minima and saddles) on the system's potential energy surface (PES). As a result, only zero-force geometry optimization (or, more generally, optimization performed at a single force value) is required by the method. In many cases, minima and transition-state saddles only exist within a range of forces and disappear beyond a certain critical point. Our method identifies such force-induced instabilities as points at which one of the Hessian eigenvalues vanishes. We elucidate the nature of those instabilities as fold and cusp catastrophes, where two or three critical points on the force-modified PES coalesce, and provide a classification of various physically distinct instability scenarios, each illustrated with a concrete chemical example. (C) 2014 AIP Publishing LLC.
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