ABSTRACT
The high-resolution (0.05 cm(-1)) spectra of gas-phase H2SO4, HDSO4, and D2SO4 were measured over the frequency region 1200-10,000 cm(-1) using Fourier-transform infrared spectroscopy. The increased resolution of this work compared with previous studies has lead to an improved vibrational analysis of H2SO4. This study has answered unresolved questions about combination bands and overlapping features from previous gas-phase spectroscopic studies of H2SO4 and marks the first experimental measurement of the nu8 and nu15 torsional vibrations in this molecule. This work leads to a brief discussion on vibrational mode mixing in sulfuric acid.
Subject(s)
Deuterium/chemistry , Spectroscopy, Fourier Transform Infrared/methods , Sulfuric Acids/chemistry , Gases , Hydrogen/chemistry , Hydrogen Bonding , Models, Statistical , Molecular Structure , Oxygen/chemistry , Pressure , Protein Conformation , Spectrophotometry/methods , Spectrophotometry, Infrared , TemperatureABSTRACT
Atmospheric field measurements and models of the stratospheric sulfate aerosol layer led to the suggestion that sulfuric acid (H2SO4) must photolyze at high altitudes. We propose that excitation of vibrational overtones of H2SO4 and its hydrate in the near-infrared and visible leads to photolysis, forming sulfur trioxide (SO3) and water. On the basis of absorption cross sections calculated with ab initio methods calibrated to experimental measurements, we estimated J values that are sufficient to explain stratospheric and mesospheric sulfur dioxide (SO2) concentrations and the observation of the sulfate layer.
