Chapter 19 - Transition path sampling

Abstract

In contrast to chemical reactions that break and make a few strong bonds, many activated processes that occur in condensed phases disrupt and reorganize hundreds of weak molecular interactions Philp and Stoddart (1996) [1], Onuchic et al. (1997) [2], Tributsch and Pohlmann (1998) [3], Agarwal and Peters (2014) [4]. The motion of individual molecules may only present barriers of order kBT, but transitions that require many degrees of freedom to simultaneously adopt unlikely and/or unfavorable configurations can still present large overall barriers. These processes are often described as having rugged potential energy surfaces (PESs) because the transition paths take many routes over many small barriers, rather than routes that all traverse the same col.