$\Delta$-Machine Learning for Potential Energy Surfaces: A PIP approach to bring a DFT-based PES to CCSD(T) Level of Theory

Abstract

``$\Delta$-machine learning" refers to a machine learning approach to bring a property such as a potential energy surface (PES) based on low-level (LL) density functional theory (DFT) energies and gradients to close to a coupled cluster (CC) level of accuracy. Here we present such an approach that uses the permutationally invariant polynomial (PIP) method to fit high-dimensional PESs. The approach is represented by a simple equation, in obvious notation $V_{LL\to CC}=V_{LL}+\Delta V_{CC-LL}$, and demonstrated for \ce{CH4}, \ce{H3O+}, and $trans$ and $cis$-$N$-methyl acetamide (NMA), \ce{CH3CONHCH3}. For these molecules, the LL PES, $V_{LL}$, is a PIP fit to DFT/B3LYP/6-31+G(d) energies and gradients, and $\Delta V_{CC-LL}$ is a precise PIP fit obtained using a low-order PIP basis set and based on a relatively small number of CCSD(T) energies. For \ce{CH4} these are new calculations adopting an aug-cc-pVDZ basis, for \ce{H3O+} previous CCSD(T)-F12/aug-cc-pVQZ energies are used, while for NMA new CCSD(T)-F12/aug-cc-pVDZ calculations are performed. With as few as 200 CCSD(T) energies, the new PESs are in excellent agreement with benchmark CCSD(T) results for the small molecules, and for 12-atom NMA training is done with 4696 CCSD(T) energies.