Transition path sampling and quantitative mechanistic hypothesis testing

Baron Peters
University of California, Santa Barbara (UC Santa Barbara)

Harmonic transition state theory, Marcus theory, RRKM theory, and classical nucleation theory exemplify the power of simple theoretical frameworks built around one-dimensional reaction coordinates. I will discuss other problems where reaction coordinates remain elusive. New versions of Transition Path Sampling (TPS) and procedures to test trial reaction coordinate will be presented. I will also present inertial likelihood maximization, a new method that works across all dynamical barrier crossing regimes. Specifically, inertial likelihood maximization identifies reaction coordinates with high transmission coefficients for inertial barrier crossing processes, and identifies coordinates that accurately predict the committor for diffusive barrier crossing processes. Examples of inertial likelihood maximization will demonstrate its value in constructing simple models of high dimensional barrier crossing processes, in computing rates, and in testing the assumptions of reaction rate theories.

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