Local and Normal Modes of OH Stretching Vibration in Hydrogen-Bonded Water Molecules

The validity of the calculation method based on the local mode in hydrogen-bonded water molecules was investigated by comparing the frequencies of the local and normal modes of OH stretching vibration in water molecules. By calculating a monomer, dimer, and trimer of water molecules using a quantum chemical ab initio theory, we examined how the frequencies of the local and normal modes and the anharmonicity of local modes vary with molecular cluster size. It was shown that, as the number of molecules increases from monomer to trimer, the anharmonicity of OH bonds increases and the difference between local and normal mode frequencies decreases. This confirms that local-mode-based calculations that can easily handle the anharmonicity can be appropriate for the calculation of the OH stretching frequency of water molecules in the condensed phase.