Structures and basicity of LiNOH (N=1-5) species

摘要

LiOH is one of the strong bases among neutral molecules. What about hydroxides of small Li-n (n=2-5) clusters? The addition of a single atom to a cluster sometimes has dramatic effects on its reactivity. This fact motivated us to perform an ab initio MP2/6-311++G(d, p) investigation on LinOH species (n=1-5). These LinOH species are stabilized by both ionic as well as covalent interactions, and are found to be stable against elimination of LiOH and OH. We have determined their gas and aqueous phase basicity by considering hypothetical protonation reactions. The calculated proton affinities of LinOH (n2) suggest their reduced basicity as compared to LiOH by 50-100 kJ/mol. The NBO charges and the highest occupied molecular orbitals also reveal the electride and alkalide characteristics of Li2OH and Li3OH, respectively. (c) 2016 Wiley Periodicals, Inc.