Theoretical investigation of water adsorption at rutile and anatase surfaces

Abstract The semiempirical MO method SINDO1 was used for the investigation of molecular and dissociative adsorption of water at titanium dioxide surfaces rutile (110) and anatase (001). The surfaces were simulated with model clusters. The influence of long-range interactions was accounted for by increase of the clusters. It was shown that a qualitatively and semiquantitatively correct description of adsorption is possible only with sufficiently large model clusters and under consideration of local relaxations. In agreement with the literature, the dissociative adsorption is energetically favored at both surfaces. For the rutile (110) surface the water adsorption was studied also in the case of oxygen defects. The adsorption energies at defect positions were found to be higher by a factor of two to three than for the ideal surface. This confirms experimental investigations which find increased activity at surfaces with defects. The local relaxation at the defect site plays an important role for the determination of relative stabilities of different adsorption sites. A potential curve was calculated for the dissociation of a water molecule adsorbed at a rutile (110) surface, and the influence of hydrogen bonding and local relaxation on the reaction barrier was determined.

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