Nitrate radical addition–elimination reactions of atmospherically relevant sulfur-containing molecules
文献信息
Joseph R. Lane, Solvejg Jørgensen, Henrik G. Kjaergaard
We have used different computational methods, including B3LYP, CCSD(T)-F12 and CBS-QB3, to study and compare the addition–elimination reaction of the nitrate radical NO3 with four sulfur-containing species relevant to atmospheric chemistry: hydrogen sulfide (H2S), dimethyl sulfide [(CH3)2S], dimethyl sulfoxide [(CH3)2SO] and sulfur dioxide (SO2). We find that the reaction with (CH3)2SO to give NO2 + (CH3)2SO2 has a very low barrier, and is likely to be the dominant oxidation mechanism for (CH3)2SO in the atmosphere. In agreement with previous experimental data and computational results, we find that the reaction with H2S and SO2 is very slow, and the reaction with (CH3)2S is not competitive with the hydrogen abstraction route. The differences in reaction energetics and rates between the four species are explained in terms of stabilizing interactions in the transition states and differences in sulfur–oxygen bond strengths.
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Physical Chemistry Chemical Physics

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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