PES and transport properties of the He⋯HBr complex from kinetic theory and molecular dynamics simulations

Abstract

The ab initio intermolecular potential of the He⋯HBr van der Waals (vdW) complex was calculated at the CCSD(T)/a5zBF level of theory and expanded in terms of the orthogonal Legendre polynomials. The PES then was implemented to calculate the interaction viscosity (η₁₂) and diffusion (D₁₂) coefficients through classical Mason–Monchick approximation (MMA), quantum mechanical close-coupling (CC), and molecular dynamics (MD) simulations. Energy-dependent Senftleben–Beenakker (SB) cross-sections were calculated using rotationally averaged cross-sections, and Boltzmann averaging was used to reveal the temperature dependence of the SB cross-sections over the temperature range of T = 50–1000 K. The calculated transport properties from MMA are in close agreement with the CC results, especially for temperatures lower than T = 900 K. The ab initio potential data then were used to derive LJ (12,6) and Vashishta MD force fields, and the equilibrium MD simulation methods were implemented to extract η₁₂ and D₁₂ coefficients using Einstein formulas. It was found that the Vashishta 3-body interaction potential model shows better accuracy than the LJ (12,6) model in MD simulations of D₁₂. For η₁₂, however, both MD potential models are successful, and an average absolute deviation of lower than 1% was obtained when compared to the quantum mechanical CC method.