摘要：

This study focuses on the interactions and reactions of silicon atoms and molecules with water. Initially, a silicon–water adduct(Si:OH2)is formed, as noticed from the red shift of theν2bending modes ofH2O,HDO, andD2O.This silicon "hydrate'' complex rearranges spontaneously through hydrogen tunneling to give HSiOH and HSiOD as final products of the reaction of Si withH2Oand HDO. Photolysis ofSi:OD2withλ400nmis necessary for the production of the deuterated insertion product DSiOD. All silicon hydroxy–hydrides undergo a photolytic decomposition reaction when strongly irradiated to give silicon monoxide and molecular hydrogen or two hydrogen atoms. Band assignments fortrans‐HSiOH,trans‐ andcis‐HSiOD, and DSiOD have been made. It appears that thecis‐isomer converts to the more stabletrans‐isomer when the matrix is heated. The SiOH bond angle has been calculated for a planar structure ofCssymmetry using the Redlich–Teller product rule and the torsional frequencies for HSiOH, HSiOD, and DSiOD. Normal coordinate analyses have been carried out using the measured frequencies for six isotopomers, namely, HSiOH, HSiOD, DSiOD,HSi18OH,HSi18OD,andDSi18OD.Thermodynamic properties have also been calculated for this new species.

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