A b i n i t i o calculations of the fundamental OH frequency of bound OH− ions

Abstract

In contrast to the OH stretching frequencies of bound H2O molecules, which are always found at lower wave numbers compared to the free molecule, the experimentally determined frequency of the OH− ion can be either lower or higher than the free-ion value. Optimized geometries and fundamental stretching frequency of OH− have been calculated here by ab initio methods at the Hartree–Fock and second-order Mo/ller–Plesset levels for a number of cation–OH−, HOH⋅⋅⋅OH−, cation–OH−⋅q−, and cation–OH−⋅OH2 complexes for Li+, Mg2+, and Al3+. The importance of electrostatic effects on the OH− frequency has been assessed by comparison with calculations of different point-charge and homogenous-field OH− systems. As long as the interaction is not dominated by electronic overlap, the frequency shift is found to be largely determined by electrostatic forces: with increasing field strength the OH− frequency rises to a maximum and then decreases. The OH− dipole moment and Mulliken charges vary monotonically with the field strength, whereas the equilibrium OH distance goes through a minimum and the bond electron density through a maximum. In strongly polarizing fields, such as in the optimized Al3+⋅OH− and Mg2+⋅OH−⋅⋅⋅OH2 systems, the OH− frequency falls below the free-ion value. Ar experimentally observed frequency downshift for an OH− ion in the condensed phase cannot be used as a criterion for the existence of H bonding. The OH− ion acts as an H-bond donor only when strongly polarized by a neighbor on its oxygen side.