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

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