Approximating Free Energy and Committor Landscapes in Standard Transition Path Sampling using Virtual Interface Exchange

Z. Faidon Brotzakis; Peter G. Bolhuis

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arXiv · 1907.04453

Approximating Free Energy and Committor Landscapes in Standard Transition Path Sampling using Virtual Interface Exchange

Z. Faidon Brotzakis·Peter G. Bolhuis

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Abstract

Transition path sampling (TPS) is a powerful technique for investigating rare transitions, especially when the mechanism is unknown and one does not have access to the reaction coordinate. Straightforward application of TPS does not directly provide the free energy landscape nor the kinetics, which motivated the development of path sampling extensions, such as transition interface sampling (TIS), and the reweighted paths ensemble (RPE), that are able to simultaneously access both kinetics and thermodynamics. However, performing TIS is more involved than TPS, and still requires (some) insight in the reaction to define interfaces. While packages that can efficiently compute path ensembles for TIS are now available, it would be useful to directly compute the free energy from a single TPS simulation. To achieve this, we developed an approximate method, denoted Virtual Interface Exchange, that makes use of the rejected pathways in a form of waste recycling. The method yields an approximate reweighted path ensemble that allows an immediate view of the free energy landscape from a single TPS, as well as enables a full committor analysis.

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Z. Faidon Brotzakis, Peter G. Bolhuis. 2019-07-09. Approximating Free Energy and Committor Landscapes in Standard Transition Path Sampling using Virtual Interface Exchange. https://arxiv.org/abs/1907.04453

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