The solvation effect on the rattling behaviour of the hydrated excess proton in water.

The solvation effect on the kinetic rattling behaviour of the hydrated excess proton H(aq) in water is theoretically modeled by using density functional theory (DFT) and the quantum chemical cluster model (CM). To test the solvation effects on the proton morphology and rattling kinetics, different solvation models for the proton are constructed based on the gas phase (GP) Zundel cation, which include the gas phase-polarizable continuum model (GP-PCM), the gas phase-supermolecule model (GP-SM), and the gas phase-supermolecule-polarizable continuum model (GP-SM-PCM). These solvation models consider either one or both of the short- and long-range solute-solvent interactions.

Density functional theory studies on the solvent effects in Al(HO) water-exchange reactions: the number and arrangement of outer-sphere water molecules.

Density functional theory (DFT) calculations combined with cluster models are performed at the B3LYP/6-311+G(d,p) level for investigating the solvent effects in Al(HO) water-exchange reactions. A "One-by-one" method is proposed to obtain the most representative number and arrangement of explicit HOs in the second hydration sphere. First, all the possible ways to locate one explicit HO in second sphere (N' = 1) based on the gas phase structure (N' = 0) are examined, and the optimal pathway (with the lowest energy barrier) for N' = 1 is determined.