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

F Aghababaei and E Nemati-Kande, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 26, 4724-4735 (2024).

DOI: 10.1039/d3cp05145e

The ab initio intermolecular potential of the HeMIDLINE HORIZONTAL ELLIPSISHBr 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 (eta 12) 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 eta 12 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 eta 12, 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. The CC solution of the Waldman-Snider equation along with the MD were used to obtain the viscosity and diffusion coefficients of HeMIDLINE HORIZONTAL ELLIPSISHBr vdW complex from an ab initio PES calculated at the CCSD(T)/aug-cc-pv5z-BF level.

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