Complexation of hydrogen peroxide with polyvinylpyrrolidone: ab initio calculations

IR spectra of thin films of a complex of polyvinylpyrrolidone (PVP) with hydrogen peroxide (1:1) were studied. The polymer complex is stable in bulk for several months, but decomposes in air. Under UV irradiation, hydrogen peroxide (absorption band 3270 cm−1) is found to convert to water (3450 cm−1). Ab initio calculations (basis set 6-31G**) reveal strong interactions in the complex of low molecular weight model PVP with five molecules of H2O2 (45 kcal mol−1), two hydrogen bonds being formed between the adjacent hydrogen peroxide molecules. The lower energies of complexation of water molecules with PVP as compared to H2O2 determine the absorption of hydrogen peroxide from water solution.