High-level ab initio calculations are performed on the coinage metal cations (Cu+, Ag+, and Au+) interacting with each of the rare gases [Rg (Rg =He to Rn)]. The RCCSD(T) procedure is employed, with basis sets being of approximately quintuple-ζ quality, but with the heavier species using relativistic effective core potentials. The interaction potentials are compared to experimental and theoretical data where they exist. In addition, transport coefficients for the mobility and diffusion of the cations in the rare gases are calculated. The latter have involved a rewriting of some of the programs used, and the required modifications are discussed. The mobility results indicate that, rather than being a rare occurrence, mobility minima may be common phenomena. Finally, a new estimate is put forward for the validity of zero-field mobilities in ion mobility spectrometry.
Journal of Chemical Physics
- Pub Date:
- October 2007
- Interatomic potentials and forces;
- Ab initio calculations;
- Coupled-cluster theory;
- Relativistic and quantum electrodynamic effects in atoms and molecules