IR spectra and ab initio calculations of poly(vinylpyrrolidone) complexes with hydrogen peroxide

Thin films of poly(vinylpyrrolidone)-hydrogen peroxide (PVP-H2O2) (1 : 1) c omplexes and urea-hydrogen peroxide inclusion complexes were studied by IR spectroscopy. UV irradiation of the polymer complex converts H2O2 into wate r. Ab initio calculations in the 6-31G** basis set revealed a strong intera ction between PVP (modeled by the monomer unit) and five H2O2 molecules (in teraction energy 188.1 kJ/mol), while the adjacent molecules of hydrogen pe roxide are linked by two virtually equivalent hydrogen bonds. The interacti on of H2O2 With the carbonyl oxygen atom (40.5 kJ/mol) is stronger than tha t of water (32.5 kJ/mol), which explains the experimentally observed bindin g of H2O2 by PVP in aqueous solutions.