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Kinetic Study of the Reactions PO + O2 and PO2 + O3 and Spectroscopy of the PO Radical

By KM Douglas, MA Blitz, TP Mangan, CM Western and JMC Plane

Abstract

The kinetics of the reactions of PO with O2 and PO2 with O3 were studied at temperatures ranging from ~ 190 to 340 K, using a pulsed laser photolysis-laser induced fluorescence technique. For the reaction of PO + O2 there is evidence of both a two- and three-body exit channel, producing PO2 + O and PO3, respectively. Potential energy surfaces of both the PO + O2 and PO2 + O3 systems were calculated using electronic structure theory, and combined with RRKM calculations to explain the observed pressure and temperature dependences. For PO + O2, at pressures typical of a planetary upper atmosphere where meteoric ablation of P will occur, the reaction is effectively pressure independent with a yield of PO2 + O of > 99%; the rate coefficient can be expressed by: log10(k, 120 – 500 K, cm3 molecule-1 s-1) = -13.915 + 2.470log10(T) - 0.5020(log10(T))2, with an uncertainty of ± 10 % over the experimental temperature range (191 – 339 K). With increasing pressure, the yield of PO3 increases, reaching ~ 90% at a pressure of 1 atm and T = 300 K. For PO2 + O3, k(188 – 339 K) = 3.7 × 10-11 exp(-1131/T) cm3 molecule-1 s-1, with an uncertainty of ± 26 % over the stated temperature range. Laser induced fluorescence spectra of PO over the wavelength range of 245 – 248 nm were collected and simulated using PGOPHER to obtain new spectroscopic constants for the ground and v = 1 vibrational levels of the X2Π and A2Σ+ states of PO

Publisher: 'American Chemical Society (ACS)'
Year: 2020
DOI identifier: 10.1021/acs.jpca.0c06106
OAI identifier: oai:eprints.whiterose.ac.uk:165257
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