The effect of machine learning predicted anharmonic frequencies on thermodynamic properties of fluid hydrogen fluoride Available to Purchase

Anharmonic effects play a crucial role in determining thermochemical properties of liquids and gases. For such extended phases, the inclusion of anharmonicity in reliable electronic structure methods is computationally extremely demanding, and hence, anharmonic effects are often lacking in thermochemical calculations. In this study, we apply the quantum cluster equilibrium method to transfer density functional theory calculations at the cluster level to the macroscopic, liquid, and gaseous phase of hydrogen fluoride. This allows us to include anharmonicity, either via vibrational self-consistent field calculations for smaller clusters or using a regression model for larger clusters. We obtain the structural composition of the fluid phases in terms of the population of different clusters as well as isobaric heat capacities as an example for thermodynamic properties. We study the role of anharmonicities for these analyses and observe that, in particular, the dominating structural motifs are rather sensitive to the anharmonicity in vibrational frequencies. The regression model proves to be a promising way to get access to anharmonic features, and the extension to more sophisticated machine-learning models is promising.