Hydrogen abstraction mechanisms and reaction rates of toluene+NO3
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| 024 | 7 | 0 | |a 10.1007/s00894-015-2749-3 |2 doi |
| 035 | |a (NATIONALLICENCE)springer-10.1007/s00894-015-2749-3 | ||
| 245 | 0 | 0 | |a Hydrogen abstraction mechanisms and reaction rates of toluene+NO3 |h [Elektronische Daten] |c [Yongmei Ma, Kehe Su, Jin Zhang, Yanli Wang, Xin Wang, Yan Liu] |
| 520 | 3 | |a The hydrogen abstraction reaction mechanisms of toluene molecule by NO3 radical were investigated theoretically with quantum chemistry and reaction kinetics. All the molecular structures, vibrational properties, and the intrinsic reaction coordinates were determined with B3LYP/6-311G(d,p). The non-dynamic electronic correlations were examined with the CASSCF dominant configurations. The energies and the potential energy profiles were refined with accurate model chemistry G3(MP2). Rate constants were determined using the CVT method over the temperature range 200-2000K. It was found that in addition to the side chain H-abstraction, the ring H-abstraction reactions are also possible. The side chain H-abstraction rate constant is in very good agreement with the available experiments and has a non-Arrhenius characteristic. Nevertheless, all the ring H-abstractions follow the Arrhenius behavior well. The over-all reaction was found to have a complex reaction mechanism in which the side chain H-abstraction is dominant below 700K while the ring H-abstractions are competitive above 800K. The approximate apparent activation energies E app are 15.5 and 66.4kJ mol-1 at 300-700K and 800-2000K, respectively. Graphical Abstract The calculation of the reaction rate indicates that the over-all reaction has a complex mechanism. The reaction proceeds mainly by the side chain H-abstraction at temperatures lower than 700 K and is nearly irreversible, while the competition of the ring H-abstractions becomes observable at higher temperatures and is reversible. | |
| 540 | |a Springer-Verlag Berlin Heidelberg, 2015 | ||
| 690 | 7 | |a Canonical variational transition-state theory |2 nationallicence | |
| 690 | 7 | |a Hydrogen abstraction |2 nationallicence | |
| 690 | 7 | |a Rate constant |2 nationallicence | |
| 690 | 7 | |a Reaction rate |2 nationallicence | |
| 690 | 7 | |a Tunneling effect |2 nationallicence | |
| 700 | 1 | |a Ma |D Yongmei |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | |
| 700 | 1 | |a Su |D Kehe |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | |
| 700 | 1 | |a Zhang |D Jin |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | |
| 700 | 1 | |a Wang |D Yanli |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | |
| 700 | 1 | |a Wang |D Xin |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | |
| 700 | 1 | |a Liu |D Yan |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | |
| 773 | 0 | |t Journal of Molecular Modeling |d Springer Berlin Heidelberg |g 21/8(2015-08-01), 1-12 |x 1610-2940 |q 21:8<1 |1 2015 |2 21 |o 894 | |
| 856 | 4 | 0 | |u https://doi.org/10.1007/s00894-015-2749-3 |q text/html |z Onlinezugriff via DOI |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 900 | 7 | |a Metadata rights reserved |b Springer special CC-BY-NC licence |2 nationallicence | |
| 908 | |D 1 |a research-article |2 jats | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-springer | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1007/s00894-015-2749-3 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Ma |D Yongmei |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Su |D Kehe |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Zhang |D Jin |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Wang |D Yanli |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Wang |D Xin |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Liu |D Yan |u Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Natural and Applied Sciences, Northwestern Polytechnical University, 710072, Xi'an, Shaanxi, People's Republic of China |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Journal of Molecular Modeling |d Springer Berlin Heidelberg |g 21/8(2015-08-01), 1-12 |x 1610-2940 |q 21:8<1 |1 2015 |2 21 |o 894 | ||