Theoretical studies on the initial reaction kinetics and mechanisms of p-, m- and o-nitrotoluene

Literature Information

Publication Date 2021-01-14
DOI 10.1039/D0CP05935H
Impact Factor 3.676
Authors

Meng Yang, Caiyue Liao, Chenglong Tang, Peng Zhang, Zuohua Huang, Jianling Li


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Abstract

The potential energy surfaces (PESs) of three nitrotoluene isomers, such as p-nitrotoluene, m-nitrotoluene, and o-nitrotoluene, have been theoretically built at the CCSD(T)/CBS level. The geometries of reactants, transition states (TSs) and products are optimized at the B3LYP/6-311++G(d,p) level. Results show that reactions of –NO2 isomerizing to ONO, and C–NO2 bond dissociation play important roles among all of the initial channels for p-nitrotoluene and m-nitrotoluene, and that the H atom migration and C–NO2 bond dissociation are dominant reactions for o-nitrotoluene. In addition, there exist pathways for three isomer conversions, but with high energy barriers. Rate constant calculations and branching ratio analyses further demonstrate that the isomerization reactions of O transfer are prominent at low to intermediate temperatures, whereas the direct C–NO2 bond dissociation reactions prevail at high temperatures for p-nitrotoluene and m-nitrotoluene, and that H atom migration is a predominant reaction for o-nitrotoluene, while C–NO2 bond dissociation becomes important by increasing the temperature.

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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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