Transfer Learning to CCSD(T): Accurate Anharmonic Frequencies from Machine Learning Models

The calculation of the anharmonic modes of small- to medium-sized molecules for assigning experimentally measured frequencies to the corresponding type of molecular motions is computationally challenging at sufficiently high levels of quantum chemical theory. Here, a practical and affordable way to calculate coupled-cluster quality anharmonic frequencies using second-order vibrational perturbation theory (VPT2) from machine-learned models is presented. The approach, referenced as NN + VPT2, uses a high-dimensional neural network (PhysNet) to learn potential energy surfaces (PESs) at different levels of theory from which harmonic and VPT2 frequencies can be efficiently determined. The NN + VPT2 approach is applied to eight small- to medium-sized molecules (H2CO, trans-HONO, HCOOH, CH3OH, CH3CHO, CH3NO2, CH 3 COOH, and CH3CONH2) and frequencies are reported from NN-learned models at the MP2/aug-cc-pVTZ, CCSD(T)/aug-cc-pVTZ, and CCSD(T)-F12/aug-cc-pVTZ-F12 levels of theory. For the largest molecules and at the highest levels of theory, transfer learning (TL) is used to determine the necessary full-dimensional, near-equilibrium PESs. Overall, NN + VPT2 yields anharmonic frequencies to within 20 cm(-1) of experimentally determined frequencies for close to 90% of the modes for the highest quality PES available and to within 10 cm(-1) for more than 60% of the modes. For the MP2 PESs only similar to 60% of the NN + VPT2 frequencies were within 20 cm(-1) of the experiment, with outliers up to similar to 150 cm(-1), compared to the experiment. It is also demonstrated that the approach allows to provide correct assignments for strongly interacting modes such as the OH bending and the OH torsional modes in formic acid monomer and the CO-stretch and OH-bend mode in acetic acid.

Automated summary

In this study, a practical and affordable method for calculating anharmonic frequencies using machine-learned models is presented, which shows high accuracy in assigning experimentally measured frequencies to molecular motions of small- to medium-sized molecules.