title: Calculated spectroscopy and atmospheric photodissociation of phosphoric acid.
abstract: Detection of phosphine (PH(3)) gas in the upper troposphere suggests that the biogeochemical P cycle also includes an atmospheric component that consists of volatile phosphorus-containing molecules. A reasonable end product for the oxidation of PH(3) in the atmosphere is phosphoric acid (H(3)PO(4)). We propose that H(3)PO(4) may be photodissociated into HOPO(2) and H(2)O in the stratosphere, where H(3)PO(4) is likely to be present in gaseous form. We have calculated the energy barrier of this reaction and show that in addition to electronic transitions, OH-stretching overtone transitions can also provide the necessary energy. OH-stretching fundamental and overtone transitions were calculated with the use of an anharmonic oscillator local mode model. The probability of overtone induced photodissociation was estimated with molecular dynamical reaction coordinate simulations. Electronic transitions were calculated with the equation of motion coupled cluster singles doubles method. We have calculated the photodissociation rate constants for absorption of visible, UV, and Lyman-alpha radiation at altitudes from 20 to 100 km. We show that at altitudes between 30 and 70 km, the photodissociation of H(3)PO(4) is likely to proceed via absorption in the UV region by electronic transitions.
authors.affiliation: Department of Chemistry, University of Otago, P.O. Box 56, Dunedin 9054, New Zealand.
authors.forename: Mivsam
authors.initials: M
authors.lastname: Yekutiel
authors.forename: Joseph R
authors.initials: JR
authors.lastname: Lane
authors.forename: Priyanka
authors.initials: P
authors.lastname: Gupta
authors.forename: Henrik G
authors.initials: HG
authors.lastname: Kjaergaard
mesh_terms: D001272:Atmosphere; D008027:Light; D008958:Models, Molecular; D008962:Models, Theoretical; D010756:Phosphoric Acids / Q000737:chemistry*; D010777:Photochemistry; D013057:Spectrum Analysis; D013816:Thermodynamics; D014732:Vibration
chemical_list: D010756:Phosphoric Acids; C030242:phosphoric acid