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RESEARCH PRODUCT
Exotic SiO(2)H(2) Isomers: Theory and Experiment Working in Harmony.
Michael C. MccarthyJürgen Gausssubject
010304 chemical physicsSiliconChemistrychemistry.chemical_element010402 general chemistry01 natural sciencesDissociation (chemistry)0104 chemical sciencesComputational chemistryMetastability0103 physical sciencesRotational spectrumPhysical chemistryGeneral Materials ScienceElectric dischargeRotational spectroscopyPhysical and Theoretical ChemistryMolecular beamConformational isomerismdescription
Replacing carbon with silicon can result in dramatic and unanticipated changes in isomeric stability, as the well-studied CO2H2 and the essentially unknown SiO2H2 systems illustrate. Guided by coupled-cluster calculations, three SiO2H2 isomers have been detected and spectroscopically characterized in a molecular beam discharge source using rotational spectroscopy. The cis,trans conformer of dihydroxysilylene HOSiOH, the ground-state isomer, and the high-energy, metastable dioxasilirane c-H2SiO2 are abundantly produced in a dilute SiH4/O2 electrical discharge, enabling precise structural determinations of both by a combination of isotopic measurements and calculated vibrational corrections. The isotopic studies also provide insight into their formation route, suggesting that c-H2SiO2 is formed promptly in the expansion but that cis,trans-HOSiOH is likely formed by secondary reactions following formation of the most stable dissociation pair, SiO + H2O. Although less abundant, the rotational spectrum of trans-silanoic acid, the silicon analogue of formic acid, HSi(O)OH, has also been observed.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2016-05-09 | The journal of physical chemistry letters |