| Abstract
| - Hafnium and zirconium atoms react with H2O2 molecules and with H2 + O2 mixtures to form M(OH)2 andM(OH)4 molecules, which are trapped in solid argon and identified from isotopic shifts in the infrared spectra.Electronic structure calculations at the MP2 level converge to almost linear M(OH)2 and tetrahedral M(OH)4molecules and predict vibrational frequencies for mixed isotopic molecules of lower symmetry that are inexcellent agreement with experimental measurements, thus substantiating the identification of hafnium andzirconium dihydroxide and tetrahydroxide molecules. Titanium atoms react to give the same product molecules,but Ti(OH)4 has an S4 structure with bent Ti−O−H bonds, Ti(OH)2 appears to be nearly linear, and the morestable tetravalent HM(O)OH isomer is more prominent for Ti. The Group 4 tetrahydroxides reported here arethe first examples of pure metal tetrahydroxide molecules.
|
