Fast Near Ab Initio Potential Energy Surfaces Using Machine Learning

A machine-learning based approach for evaluating potential energies for quantum mechanical studies of properties of the ground and excited vibrational states of small molecules is developed. This approach uses the molecular-orbital-based machine learning (MOB-ML) method to generate electronic energies with the accuracy of CCSD(T) calculations at the same cost as a Hartree-Fock calculation. To further reduce the computational cost of the potential energy evaluations without sacrificing the CCSD(T) level accuracy, GPU-accelerated Neural Network Potential Energy Surfaces (NN-PES) are trained to geometries and energies that are collected from small-scale Diffusion Monte Carlo (DMC) simulations, which are run using energies evaluated using the MOB-ML model. The combined NN+(MOB-ML) approach is used in variational calculations of the ground and low-lying vibrational excited states of water and in DMC calculations of the ground states of water, CH5+, and its deuterated analogues. For both of these molecules, comparisons are made to the results obtained using potentials that were fit to much larger sets of electronic energies than were required to train the MOB-ML models. The NN+(MOB-ML) approach is also used to obtain a potential surface for C2H5+, which is a carbocation with a nonclassical equilibrium structure for which there is currently no available potential surface. This potential is used to explore the CH stretching vibrations, focusing on those of the bridging hydrogen atom. For both CH5+ and C2H5+ the MOB-ML model is trained using geometries that were sampled from an AIMD trajectory, which was run at 350 K. By comparison, the structures sampled in the ground state calculations can have energies that are as much as ten times larger than those used to train the MOB-ML model. For water a higher temperature AIMD trajectory is needed to obtain accurate results due to the smaller thermal energy. A second MOB-ML model for C2H5+ was developed with additional higher energy structures in the training set. The two models are found to provide nearly identical descriptions of the ground state of C2H5+.

Automated summary

A machine-learning based approach is developed for evaluating potential energies of small molecules, allowing for quantum mechanical studies of their ground and excited vibrational states. The approach combines molecular-orbital-based machine learning and GPU-accelerated neural network potential energy surfaces to generate accurate electronic energies at a lower computational cost. The method is applied to variational calculations and diffusion Monte Carlo calculations of water, CH5+, and its deuterated analogues, yielding satisfactory results compared to potentials fit to larger sets of electronic energies.