TY - JOUR
T1 - Calculated Spectroscopy and Atmospheric Photodissociation of Phosphoric acid
AU - Yekutiel, M.
AU - Lane, J. R.
AU - Gupta, P.
AU - Kjærgaard, Henrik Grum
PY - 2010/7/22
Y1 - 2010/7/22
N2 - Detection of phosphine (PH3) 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 PH3 in the atmosphere is phosphoric acid (H3PO4). We propose that H3PO4 may be photodissociated into HOPO2 and H2O in the stratosphere, where H3PO4 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-α radiation at altitudes from 20 to 100 km. We show that at altitudes between 30 and 70 km, the photodissociation of H 3PO4 is likely to proceed via absorption in the UV region by electronic transitions.
AB - Detection of phosphine (PH3) 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 PH3 in the atmosphere is phosphoric acid (H3PO4). We propose that H3PO4 may be photodissociated into HOPO2 and H2O in the stratosphere, where H3PO4 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-α radiation at altitudes from 20 to 100 km. We show that at altitudes between 30 and 70 km, the photodissociation of H 3PO4 is likely to proceed via absorption in the UV region by electronic transitions.
M3 - Journal article
SN - 1089-5639
VL - 114
SP - 7544
EP - 7552
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
ER -