Self-learning hybrid Monte Carlo method for isothermal-isobaric ensemble: Application to liquid silica.

Self-learning hybrid Monte Carlo (SLHMC) is a first-principles simulation that allows for exact ensemble generation on potential energy surfaces based on density functional theory. The statistical sampling can be accelerated with the assistance of smart trial moves by machine learning potentials. In the first report [Nagai et al., Phys. Rev. B 102, 041124(R) (2020)], the SLHMC approach was introduced for the simplest case of canonical sampling. We herein extend this idea to isothermal–isobaric ensembles to enable general applications for soft materials and liquids with large volume fluctuation. As a demonstration, the isothermal–isobaric SLHMC method was used to study the vibrational structure of liquid silica at temperatures close to the melting point, whereby the slow diffusive motion is beyond the time scale of first-principles molecular dynamics. It was found that the static structure factor thus computed from first-principles agrees quite well with the high-energy x-ray data.