Molecular structures and properties of HGeX + and HXGe + (X=O, S, Se) species

Abstract

Ab initio molecular orbital calculations were carried out on HGeX + and HXGe + ions (X=O, S, Se). Equilibrium geometries of the studied species were located at the HF and MP2 levels using valence triple-ζ basis set with two sets of p-polarization functions on hydrogens and two sets of d-polarization functions on heavier elements (TZP basis set). At both levels bent conformations of HXGe + ions are found to be the global minimum structures and HGeX + ions are local minimum species. The predicted bent conformations for HXGe + ions are in contradiction to the Walsh's rules, which require linear structures for the HXY molecules possessing ten valence electrons. The MP4/TZP/MP2/TZP level of calculations for the possible dissociation products (GeX, H + and GeX +, H) predicts that all title compounds are thermodynamically stable and should be observed by experimentalists. To assist such experimental studies on these experimentally elusive ions, we furnish reliable theoretical molecular parameters, rotational constants, vibrational frequencies and intensities.