Δ-Machine Learning to Elevate DFT-Based Potentials and a Force Field to the CCSD(T) Level Illustrated for Ethanol

Abstract

Progress in machine learning has facilitated the development of potentials that offer both the accuracy of first-principles techniques and vast increases in the speed of evaluation. Recently, Δ-machine learning has been used to elevate the quality of a potential energy surface (PES) based on low-level, e.g., density functional theory (DFT) energies and gradients to close to the gold-standard coupled cluster level of accuracy. We have demonstrated the success of this approach for molecules, ranging in size from H 3 O + to 15-atom acetyl-acetone and tropolone. These were all done using the B3LYP functional. Here, we investigate the generality of this approach for the PBE, M06, M06-2X, and PBE0 + MBD functionals, using ethanol as the example molecule. Linear regression with permutationally invariant polynomials is used to fit both low-level and correction PESs. These PESs are employed for standard RMSE analysis for training and test data sets, and then general fidelity tests such as energetics of stationary points, normal-mode frequencies, and torsional potentials are examined. We achieve similar improvements in all cases. Interestingly, we obtained significant improvement over DFT gradients where coupled cluster gradients were not used to correct the low-level PES. Finally, we present some results for correcting a recent molecular mechanics force field for ethanol and comment on the possible generality of this approach.