Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 2007-03-22

Spectroscopic and DFT study of tungstic acid peroxocomplexes.

Laura Barrio, José M Campos-Martín, José L G Fierro

Index: J. Phys. Chem. A 111(11) , 2166-71, (2007)

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Abstract

The catalytic system formed by tungstic acid and its complexes with H2O2 and phenylphosphonic acid has been analyzed from the experimental and theoretical points of view. Previous structural studies by XRD proved the validity of the DFT proposed models and methodology. Hydrogen peroxide reacts with tungstic acid to form a peroxo complex. Vibrational and electronic spectra showed significant changes upon interaction with H2O2. The DFT and TD-DFT for IR and UV-vis calculations not only are in agreement with experimental data but also allow for a deeper characterization of the species formed in in situ conditions. A SCRF/PCM methodology was chosen to account for the solvent effect. The solvent effect of water was considered for geometry re-optimization of the structure and for the TD-DFT calculations.