Assessing Many-Body Effects of Water Self-Ions. I: OH-(H2O) n Clusters.

Abstract

The importance of many-body effects in the hydration of the hydroxide ion (OH-) is investigated through a systematic analysis of the many-body expansion of the interaction energy carried out at the CCSD(T) level of theory, extrapolated to the complete basis set limit, for the low-lying isomers of OH-(H2O) n clusters, with n = 1-5. This is accomplished by partitioning individual fragments extracted from the whole clusters into "groups" that are classified by both the number of OH- and water molecules and the hydrogen bonding connectivity within each fragment. With the aid of the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA) method, this structure-based partitioning is found to largely correlate with the character of different many-body interactions, such as cooperative and anticooperative hydrogen bonding, within each fragment. This analysis emphasizes the importance of a many-body representation of inductive electrostatics and charge transfer in modeling OH- hydration. Furthermore, the rapid convergence of the many-body expansion of the interaction energy also suggests a rigorous path for the development of analytical potential energy functions capable of describing individual OH--water many-body terms, with chemical accuracy. Finally, a comparison between the reference CCSD(T) many-body interaction terms with the corresponding values obtained with various exchange-correlation functionals demonstrates that range-separated, dispersion-corrected, hybrid functionals exhibit the highest accuracy, while GGA functionals, with or without dispersion corrections, are inadequate to describe OH--water interactions.