Experimental Study of the Removal of Ground- and Excited-State Phosphorus Atoms by Atmospherically Relevant Species.
J Phys Chem A
; 123(44): 9469-9478, 2019 Nov 07.
Article
em En
| MEDLINE
| ID: mdl-31603680
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 â¼200 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.
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2019
Tipo de documento:
Article
País de afiliação:
Reino Unido