Quasiclassical Trajectory Simulation as a Protocol to Build Locally Accurate Machine Learning Potentials.

Abstract

Direct trajectory calculations have become increasingly popular in recent computational chemistry investigations. However, the exorbitant computational cost of ab initio trajectory calculations usually limits its application in mechanistic explorations. Recently, machine learning-based potential energy surface (ML-PES) provides a powerful strategy to circumvent the heavy computational cost and meanwhile maintain the required accuracy. Despite the appealing potential, constructing a robust ML-PES is still challenging since the training set of the PES should cover a broad enough configuration space. In this work, we demonstrate that when the concerned properties could be collected by the localized sampling of the configuration space, quasiclassical trajectory (QCT) calculations can be invoked to efficiently obtain locally accurate ML-PESs. We prove our concept with two model reactions: methyl migration of i-pentane cation and dimerization of cyclopentadiene. We found that the locally accurate ML-PESs are sufficiently robust for reproducing the static and dynamic features of the reactions, including the time-resolved free energy and entropy changes, and time gaps.