Investigations of the structure of H2O clusters adsorbed on TiO2 surfaces by near-infrared absorption spectroscopy.

The overtone and combination bands of the fundamental vibration modes (nu(1), symmetric stretching; nu(2), bending; and nu(3), asymmetric stretching) attributed to the H(2)O molecules adsorbed on a TiO(2) surface could be observed in the near-infrared (NIR) region. Especially, two absorption bands attributed to the combination (nu(2) + nu(3)) and (nu(1) + nu(3)) modes of the H(2)O molecules adsorbed on the TiO(2) surface were observed at around 1940 and 1450 nm, respectively. From detailed investigations on the (nu(2) + nu(3)) combination band, it was found that H(2)O molecules absorbed on a TiO(2) surface aggregate to form clusters due to the high surface tension of H(2)O arising from the intermolecular hydrogen bonds, and the hydrogen-bonded H(2)O in the bulk part of the cluster and the hydrogen-bond-free H(2)O in the outside spherical part of the cluster could be easily distinguished. Furthermore, it was quantitatively confirmed that the relaxation of the surface energy accompanying the adsorption of H(2)O on the TiO(2) surface stabilized the adsorption states of the hydrogen-bonded H(2)O molecules, while on the other hand, the hydrogen-bond-free H(2)O molecules became unstable as compared to the liquid-phase H(2)O molecules.