Reactions of group IV metal atoms with water molecules. Matrix isolation FTIR and theoretical studies

Laser-ablated group IV metal atoms have been co-deposited at 11 K with water molecules in excess argon. The metal atoms reacted with water to form the insertion product HMOH and H2M(OH)(2) (M = Ti, Zr, Hf) molecules spontaneously. Photolysis of the HTiOH species produced the H2TiO molecule as well as the TiO monoxide. In the cases of Zr and Hf, however, the H2ZrO and N2HfO molecules were produced on annealing, and the H-2 elimination process was not observed on photolysis. In addition, the HMO species were also observed and identified. The aforementioned species were identified via isotopic substitutions as well as theoretical frequency calculations. Qualitative analysis of the possible reaction paths leading to the observed products is proposed.