Pt(II)-Ion Hydration: Structural and Vibrational Characteristics from Theory and Experiment

IR, Raman measurements, and ab initio molecular dynamics simulations have been carried out to describe and understand the structural and dynamic behavior of hydrated Pt2+ ion in water. The experiments have revealed strong red-shifted O-H bond frequencies and blue-shifted ligand deformation bands. The simulations have showed that the presence of the doubly charged cation and the enhanced hydrogen bond formations between the first and second shells result in significant structural changes in the first solvation shell, which in turn yield the characteristic shifts in the vibrational spectra. The weakening of the ligand O-H bonds and the strengthened hydrogen-bonds around the cation can be accounted for as the result of the strong Coulombic field of the Pt(II)-ion. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 109: 2591-2598, 2009