Improved techniques for the calculation of ab initio ion-neutral interaction potentials: application to coinage metal ions interacting with rare gas atoms

Abstract

Ab initio values for the potential energy functions for ion–neutral interactions can be tested by comparison with gaseous ion transport coefficients, but only if special care is taken to compute the interaction potentials accurately over wide ranges of internuclear separation. This is illustrated here by a reanalysis of the ab initio values for the coinage metal ions interacting with rare gas atoms, precise calculations of the transport cross sections over extremely wide ranges of energy, and similarly precise calculations of the zero-field ion mobilities as functions of gas temperature and the field-dependent ion mobilities at various fixed temperatures. The calculations indicate that the mobilities for Ag+(1S) moving in Ne or Ar can distinguish between the existing, very similar ab initio potentials. They also show that substantial differences exist among the mobilities of the coinage metal anions and the ground and excited states of the cations. The techniques implemented are recommended for future ab initio calculations.