Comparison of Eight Classical Lennard-Jones-Based H₂ Molecular Models in the Gas Phase at Temperatures and Pressures...

This work compares eight classical H₂ molecular models in the gas phase taken from the existing literature. All models are based on Lennard-Jones (LJ) 12-6 terms for the van der Waals interactions and hence easier to transfer to multiphase molecular simulations than more sophisticated potentials. The H₂ potentials tested include one-site, two-site, three-site, and five-site models, with the sites being either the H atoms, the center-of-mass of the H₂ molecule, or massless sites. For the multisite models, high-frequency H-H stretching modes can lead to poor equipartition of the kinetic energy, and the timestep for molecular dynamics (MD) simulations should be reduced to maintain a stable numerical integration of the equations of motion. As such, only those models with rigid bonds are considered. In the present case, 600 MD simulations of H₂ gas were carried out over a large range of temperatures (-50 to +90 °C) and at densities corresponding to a pressure range of 50 to 2000 bar, which include the operating conditions of on-board storage tanks in hydrogen-fueled vehicles. Most of the models under study were found to reproduce reasonably well the experimental pVT phase diagram as well as the solubility. Discrepancies only became significant at the highest densities tested, and these could be used to rank the different models. All model diffusion coefficients were essentially indistinguishable from experimental results, and as such, kinetically dominated dynamic properties could not be used as a criterion for the choice of model. Among the eight models tested, two of them, i.e., the two-site model of Yang and Zhong and the one-site model derived from Buch performed very well over the range of conditions tested. They represent a good compromise between realism, simplicity, and computational efficiency.