Douglas, KM orcid.org/0000-0002-3281-3685, Blitz, MA orcid.org/0000-0001-6710-4021, Mangan, TP orcid.org/0000-0001-7053-5594 et al. (1 more author) (2019) Experimental Study of the Removal of Ground and Excited State Phosphorus Atoms by Atmospherically Relevant Species. The Journal of Physical Chemistry A, 123 (44). pp. 9469-9478. ISSN 1089-5639
Abstract
The reaction kinetics of the ground and first two excited states of atomic phosphorus, P, with atmospherically relevant species were studied at temperatures ranging from ∼200 to 750 K using a pulsed laser photolysis-laser-induced fluorescence technique. The temperature dependence of the rate coefficients is parametrized as follows (units: cm3 molecule–1 s–1, 1σ errors): k(P(2P)+O2)(189 ≤ T/K ≤ 701) = (7.10 ± 1.03) × 10–12 × (T/298)1.42±0.13 × exp[(374 ± 41)/T]; k(P(2D)+O2)(188 ≤ T/K ≤ 714) = (1.20 ± 0.29) × 10–11 × (T/298)0.821±0.207 × exp[(177 ± 70)/T]; k(P(2D)+CO2)(296 ≤ T/K ≤ 748) = (5.68 ± 0.36) × 10–12 × (T/298)0.800±0.103; k(P(2D)+N2)(188 ≤ T/K ≤ 748) = (1.42 ± 0.03) × 10–12 × (T/298)1.36±0.04; k(P(4S)+O2)(187 ≤ T/K ≤ 732) = (3.08 ± 0.31) × 10–13 × (T/298)2.24±0.29. Electronic structure theory combined with RRKM calculations have been used to explain the unusual temperature dependence of P(4S) + O2. The small pre-exponential factor for the reaction results from a tight steric constraint, together with the requirement that the reaction occurs on doublet rather than sextet electronic surfaces.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | (c) 2019, American Chemical Society. This is an author produced version of a paper published in The Journal of Physical Chemistry A. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 30 Oct 2019 16:04 |
Last Modified: | 11 Oct 2020 00:38 |
Status: | Published |
Publisher: | American Chemical Society (ACS) |
Identification Number: | 10.1021/acs.jpca.9b07855 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:152552 |