A highly accurate full-dimensional ab initio potential surface for the rearrangement of methylhydroxycarbene (H3C–C–OH)

Abstract

We report here a full-dimensional machine learning global potential surface (PES) for the rearrangement of methylhydroxycarbene (H₃C–C–OH, 1t). The PES is trained with the fundamental invariant neural network (FI-NN) method on 91 564 ab initio energies calculated at the UCCSD(T)-F12a/cc-pVTZ level of theory, covering three possible product channels. FI-NN PES has the correct symmetry properties with respect to permutation of four identical hydrogen atoms and is suitable for dynamics studies of the 1t rearrangement. The averaged root mean square error (RMSE) is 11.4 meV. Six important reaction pathways, as well as the energies and vibrational frequencies at the stationary geometries on these pathways are accurately preproduced by our FI-NN PES. To demonstrate the capacity of the PES, we calculated the rate coefficient of hydrogen migration in –CH₃ (path A) and hydrogen migration of –OH (path B) with instanton theory on this PES. Our calculations predicted the half-life of 1t to be 95 min, which is excellent in agreement with experimental observations.