Experimental and theoretical study of the recombination reactions of FS(O2)O with FC(O)O and CO

Literature Information

Publication Date 2001-04-23
DOI 10.1039/B100348H
Impact Factor 3.676
Authors

M. E. Tucceri, M. P. Badenes, A. E. Croce, C. J. Cobos


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Abstract

The laser flash photolysis technique has been used to study the kinetics of the reactions of FS(O2)O with FC(O)O and CO at 296 K. Both reactions were found to be essentially in the second-order regime at total pressures ranging from 160 to 1020 mbar of the radical precursors FS(O2)OF, CO and O2 and the bath gas SF6. The FS(O2)O and FC(O)O radicals were monitored by absorption spectroscopy at 450 and 545 nm. The determined limiting high pressure rate coefficients for the FC(O)O + FS(O2)O → FC(O)OO(O2)SF and FS(O2)O + CO → FS(O2)OCO reactions are 1.0 ± 0.1 × 10−12 and 4.3 ± 0.9 × 10−17 cm3 molecule−1 s−1. Employing isodesmic reaction schemes with total energies calculated at the B3LYP/6-311++G(3df,p)//B3LYP/6-311++G(d,p) level of theory, enthalpies of formation for FS(O2)O, FS(O2)O2, FS(O2)OF, FS(O2)OCO, FS(O2)OC(O)CO, FS(O2)OC(O)O2, FC(O)OO(O2)SF, FCO, FC(O)O and FC(O)O2 molecules were derived. An analysis of the rate coefficients in terms of the statistical adiabatic channel model and the transition state theory on potential energy surfaces derived from density functional theory calculations has been carried out.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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