Characterization of dynamics and reactivities of solvated ions byab initiosimulations

Abstract
Based on a systematic investigation of trajectories of ab initio quantum mechanical/molecular mechanical simulations of numerous cations in water a standardized procedure for the evaluation of mean ligand residence times is proposed. For the characterization of reactivity and structure-breaking/structure-forming properties of the ions a measure is derived from the mean residence times calculated with different time limits. It is shown that ab initio simulations can provide much insight into ultrafast dynamics that are presently not easily accessible by experiment. © 2003 Wiley Periodicals, Inc. J Comput Chem 25: 211–217, 2004