Ab initio X(1)0(+) ground state potential curves of Pb···RG dimers (RG = He, Ne, Ar) including spin-orbit effects. Simulation of diffusion coefficients.

Abstract

CCSD(T) ground state potential curves of Pb···RG systems (RG = He, Ne and Ar) are presented and the importance of the inclusion of spin-orbit effects is discussed. The closed-shell character of the Pb atom at the two-component relativistic level of relativistic theory leads to shallower potential energy curves compared to scalar relativistic open-shell calculations. The pressure-independent cross-diffusion coefficients pD12 have been simulated using the extrapolated two-component CCSD(T) ground state potential curves. The diffusion coefficients from scattering theory are compared with simulations based on molecular dynamics (MD) using the velocity autocorrelation function (VACF) and the Einstein equation. A correction for the proper assessment of the uncertainty in the VACF is proposed. The acceleration of the MD simulation of Pb in RG diffusion is proposed utilizing the RG in Pb diffusion. The dU[TQ]Z/CCSD(T) potential curve of Pb···He (De = 8.667 cm(-1), re = 4.683 Å) supports only one vibrational level. The anharmonicity of this potential is compared to the potential of He···He which also supports only one vibrational level. The comparison is based on the mean square separations of the vibrational wave function.