New trends along hydrogen polyoxides: unusually long oxygen-oxygen bonds in H2O6 and H2O7

作者：Denis Pablo A^*; Pereyra Huelmo C

来源：Molecular Physics, 2014, 112(23): 3047-3056.

DOI：10.1080/00268976.2014.928385

• infrared spectroscopy
• thermochemistry
• polyoxides
• coupled cluster theory
• density functional theory

By means of coupled cluster, G4 and B3LYP calculations, we characterised polyoxides H2O6 and H2O7. These two molecules behave very differently from lower polyoxides, given that some isomers present unusual bonding. In the case of H2O6, the central OO bond is predicted, to be 1.909 angstrom, at the CCSD(T)/cc-pVTZ level. Two conformational isomers of H2O6 display nearly the same enthalpy of formation, but only one of them has extremely long OO bonds. For H2O7, the most stable isomer also has two unusually long OO bonds. At the CCSD(T) level, and after extrapolation to the complete basis set limit, this isomer is predicted to be 5.37 kcal mol(-1) more stable than the one with short OO bonds, and the longest OO bond distance is expected to be close to 1.96 angstrom. Analysis of correlation energies indicated that the new isomers found for H2O6 and H2O7 are among the most strongly correlated molecules that can be formed with first-row atoms.

• 出版日期2014-12-2