Ibrahim Alexander, Roy Pierre-Nicholas
Department of Physics and Astronomy, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada.
Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2L 3G1, Canada.
J Chem Phys. 2022 Nov 7;157(17):174503. doi: 10.1063/5.0120169.
We present the equation of state of solid parahydrogen between 0.024 and 0.1 Å at T = 4.2 K, calculated using path integral Monte Carlo simulations, with ab initio two-body and three-body interaction potentials. We correct for finite size simulation errors using potential tail corrections. Trotter factorization errors are accounted for either via extrapolation or by using a suitably small imaginary time step. We incorporate the three-body interaction using two methods: (1) the full inclusion method, where pair and three-body interactions are used in both Monte Carlo sampling and in the energy estimators, and (2) the perturbative method, where three-body interactions are omitted from sampling but are still present in energy estimations. Both treatments of the three-body interaction return very similar total energies and pressures. The presence of three-body interactions has only minor effects on the structural properties of the solid. Whereas the pair interaction, on its own, significantly overestimates the pressure of solid parahydrogen, the additional presence of the three-body interaction causes a severe underestimation of the pressure. Our findings suggest that accurate simulations of solid parahydrogen require four-body and possibly higher-order many-body interactions. It may also be the case that static interaction potentials are entirely unsuitable for simulations of solid parahydrogen at high densities.
