Distinct molecular dynamics dividing liquid-like and gas-like supercritical hydrogens

Abstract

Understanding how a supercritical fluid is related to normal liquid and gas and separating it into liquid-like and gas-like regions are of fundamental and practical importance. Despite the usefulness of hydrogen storage, molecular dynamics images on supercritical hydrogens exhibiting strong nuclear quantum effects are scarce. Taking advantage of the non-empirical ab initio molecular dynamics method for hydrogen molecules, we found that, while radial distribution functions and diffusion show a monotonic change along the density, van Hove time correlation functions and intramolecular properties such as bond length and vibrational frequency exhibit the anomalous order crossing the Widom line. By demonstrating that the anomalous order stemmed from the largest deviations between liquid-like and gas-like solvations formed around the Widom line, we concluded that this supercritical fluid is a mixture of liquid and gas possessing heterogeneity. The obtained physical insights can be an index to monitor the supercriticality and to identify distinct liquid-like and gas-like supercritical fluids.