# Theoretical Study of Microscopic Solvation of Lithium in Water
Clusters: Neutral and Cationic Li(H_{2}O)_{n} (*n* = 1−6 and 8)

_{n}

journal contribution

posted on 01.04.1998, 00:00 by Kenro Hashimoto, Tetsuya KamimotoThe structure, stability, and electronic state of
Li(H

_{2}O)*(*_{n}*n*= 1−6 and 8) clusters have been investigated by an*ab initio*molecular orbital method, including electron correlation, and compared with those of their cations. The*interior*structure where the Li atom is surrounded by four H_{2}O molecules in the first shell and more in the second shell is found to be the most stable for both neutral and cationic*n*≥ 4 clusters. The size dependence of the vertical ionization potentials of Li(H_{2}O)*is in good agreement with the recent experiment. It decreases successively until*_{n}*n*= 4 and becomes nearly constant for*n*≥ 4 being close to the bulk limit of vertical detachment energies of (H_{2}O)_{n}^{-}. The excess electron is separated from Li and distributed outside the first-shell cavity in*n*≥ 4 clusters. The electronic state of the clusters changes from a one-center atomic state for*n*≤ 3 to a two-center ionic state for*n*≥ 4 with a gradual localization of the excess electron. Dangling hydrogens interacting with the excess electron play a role as actuators of the*surface*state.