Spectroscopy and photochemistry of hydrogen peroxide and its complexes in solid rare gases

Molecules and atoms can be isolated in low temperature solids, and this offers an opportunity to study their properties in monomeric and complexed forms, and in photochemical reactions. Hydrogen peroxide is an important molecule in various oxidation reactions in industrial chemistry and in the atmosphere. In this thesis, the vibrational properties, structure, and photochemistry of hydrogen peroxide and its complexes have been studied in solid rare gases using infrared and luminescence spectroscopy. Quantum chemical calculations have been carried out to interpret the experimental results. Hydrogen peroxide was obtained from urea hydrogen peroxide adduct compound by flushing it with rare gas. This newly-developed method provides a safe and convenient means of producing pure, gaseous hydrogen peroxide for laboratory studies. The IR spectra of H2O2, HDO2, and D2O2 in solid argon are presented and compared with previous results, and the IR spectra in solid krypton and xenon are presented for the first time. Complexes of hydrogen peroxide with small atmospheric species, such as SO2 and N2 were studied using infrared spectroscopy and quantum chemical calculations. UV photolysis of hydrogen peroxide in solid argon produces a complex between water and a ground state oxygen atom, and OH radicals. It is found that the H2O···O(P) complex can be converted back to hydrogen peroxide by light. A three-component photokinetic model