Supervised learning and the finite-temperature string method for computing committor functions and reaction rates

• Published in: The Journal of chemical physics Vol. 157; no. 18; pp. 184111 - 184138
• Main Authors: Hasyim, Muhammad R., Batton, Clay H., Mandadapu, Kranthi K.
• Format: Journal Article
• Language: English
• Published: Melville American Institute of Physics 14.11.2022
• Subjects: Algorithms; Error analysis; Feedback loops; Finite element method; Importance sampling; Machine learning; Molecular dynamics; Neural networks; Potential energy; Strings; Supervised learning; Training
• ISSN: 0021-9606; 1089-7690; 1520-9032; 1089-7690
• DOI: 10.1063/5.0102423

A central object in the computational studies of rare events is the committor function. Though costly to compute, the committor function encodes complete mechanistic information of the processes involving rare events, including reaction rates and transition-state ensembles. Under the framework of transition path theory, Rotskoff et al. [Proceedings of the 2nd Mathematical and Scientific Machine Learning Conference, Proceedings of Machine Learning Research (PLMR, 2022), Vol. 145, pp. 757–780] proposes an algorithm where a feedback loop couples a neural network that models the committor function with importance sampling, mainly umbrella sampling, which collects data needed for adaptive training. In this work, we show additional modifications are needed to improve the accuracy of the algorithm. The first modification adds elements of supervised learning, which allows the neural network to improve its prediction by fitting to sample-mean estimates of committor values obtained from short molecular dynamics trajectories. The second modification replaces the committor-based umbrella sampling with the finite-temperature string (FTS) method, which enables homogeneous sampling in regions where transition pathways are located. We test our modifications on low-dimensional systems with non-convex potential energy where reference solutions can be found via analytical or finite element methods, and show how combining supervised learning and the FTS method yields accurate computation of committor functions and reaction rates. We also provide an error analysis for algorithms that use the FTS method, using which reaction rates can be accurately estimated during training with a small number of samples. The methods are then applied to a molecular system in which no reference solution is known, where accurate computations of committor functions and reaction rates can still be obtained.