Dynamics of ion solvation. Li++H2O→Li+(H2O)*

Abstract

The classical trajectory method has been used to calculate the primary cross section for Li⁺+H₂O recombination versus relative translational energy. The criterion used for the formation of a vibrationally and rotationally excited Li⁺(H₂O)^* cluster is the presence of more than one inner turning point in the Li⁺+H₂O relative distance. As the relative translational energy is increased, there is a dramatic decrease in the primary cross section. It is 542 Ų at E_rel = 0.5 kcal/mole and essentially zero at E_rel = 5.0 kcal/mole. The results are discussed in terms of the inefficiency of intramolecular energy transfer from the Li⁺+H₂O relative motions to the H₂O vibrational and rotational degrees of freedom.