An Ab Initio Neural Network Potential Energy Surface for the Dimer of Formic Acid and Further Quantum Tunneling Dynamics.

Abstract

We construct a full-dimensional ab initio neural network potential energy surface (PES) for the isomerization system of the formic acid dimer (FAD). This is based upon ab initio calculations using the DLPNO-CCSD(T) approach with the aug-cc-pVTZ basis set, performed at over 14000 symmetry-unique geometries. An accurate fit to the obtained energies is generated using a general neural network fitting procedure combined with the fundamental invariant method, and the overall energy-weighted root-mean-square fitting error is about 6.4 cm-1. Using this PES, we present a multidimensional quantum dynamics study on tunneling splittings with an efficient theoretical scheme developed by our group. The ground-state tunneling splitting of FAD calculated with a four-mode coupled method is in good agreement with the most recent experimental measurements. The PES can be applied for further dynamics studies. The effectiveness of the present scheme for constructing a high-dimensional PES is demonstrated, and this scheme is expected to be feasible for larger molecular systems.