Predicting Frequency from the External Chemical Environment: OH Vibrations on Hydrated and Hydroxylated Surfaces

Robust correlation curves are essential to decipher structural information from IR-vibrational spectra. However, for surface-adsorbed water and hydroxides, few such correlations have been presented in the literature. In this paper, OH vibrational frequencies are correlated against 12 structural descriptors representing the quantum mechanical or geometrical environment, focusing on those external to the vibrating molecule. A nonbiased fitting procedure based on Gaussian process regression (GPR) was used alongside simple analytical functional forms. The training data consist of 217 structurally unique OH groups from 38 water/metal oxide interface systems for MgO, CaO and CeO₂, all optimized at the DFT level, and the fully anharmonic and uncoupled OH vibrational signatures were calculated. Among our results, we find the following: (i) The intermolecular R(H···O) hydrogen bond distance is particularly strong, indicating the primary cause of the frequency shift. (ii) Similarly, the electric field along the H-bond vector is also a good descriptor. (iii) Highly detailed machine learning descriptors (ACSF, SOAP) are less intuitive but were found to be more capable descriptors. (iv) Combinations of geometric and QM descriptors give the best predictions, supplying complementary information.