Masia, Marco and Probst, Michael and Rey, Rossend (2005) On the performance of molecular polarization methods. II. Water and carbon tetrachloride close to a cation. The Journal of Chemical Physics, Vol. 123 (16), p. 1-13. eISSN 1089-7690. Article.
Our initial study on the performance of molecular polarization methods close to a positive point charge [M. Masia, M. Probst, and R. Rey, J. Chem. Phys. 121, 7362 (2004)] is extended to the case in which a molecule interacts with a real cation. Two different methods (point dipoles and shell model) are applied to both the ion and the molecule. The results are tested against high-level ab initio calculations for a molecule (water or carbon tetrachloride) close to Li+, Na+, Mg2+, and Ca2+. The monitored observable is in all cases the dimer electric dipole as a function of the ion-molecule distance for selected molecular orientations. The moderate disagreement previously obtained for point charges at intermediate distances, and attributed to the linearity of current polarization methods (as opposed to the nonlinear effects evident in ab initio calculations), is confirmed for real cations as well. More importantly, it is found that at short separations the phenomenological polarization methods studied here substantially overestimate the dipole moment induced if the ion is described quantum chemically as well, in contrast to the dipole moment induced by a point-charge ion, for which they show a better degree of accord with ab initio results. Such behavior can be understood in terms of a decrease of atomic polarizabilities due to the repulsion between electronic charge distributions at contact separations. It is shown that a reparametrization of the Thole method for damping of the electric field, used in conjunction with any polarization scheme, allows to satisfactorily reproduce the dimer dipole at short distances. In contrast with the original approach (developed for intramolecular interactions), the present reparametrization is ion and method dependent, and corresponding parameters are given for each case.
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