caa a22 4500 60551285X CHVBK 20210128100657.0 cr unu---uuuuu 210128e20150801xx s 000 0 eng 10.1007/s00894-015-2749-3 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2749-3 Hydrogen abstraction mechanisms and reaction rates of toluene+NO3 [Elektronische Daten] [Yongmei Ma, Kehe Su, Jin Zhang, Yanli Wang, Xin Wang, Yan Liu] 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. Springer-Verlag Berlin Heidelberg, 2015 Canonical variational transition-state theory nationallicence Hydrogen abstraction nationallicence Rate constant nationallicence Reaction rate nationallicence Tunneling effect nationallicence Ma Yongmei 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 aut Su Kehe 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 aut Zhang Jin 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 aut Wang Yanli 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 aut Wang Xin 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 aut Liu Yan 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 aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/8(2015-08-01), 1-12 1610-2940 21:8<1 2015 21 894 https://doi.org/10.1007/s00894-015-2749-3 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2749-3 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ma Yongmei 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 aut NATIONALLICENCE 700 1- Su Kehe 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 aut NATIONALLICENCE 700 1- Zhang Jin 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 aut NATIONALLICENCE 700 1- Wang Yanli 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 aut NATIONALLICENCE 700 1- Wang Xin 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 aut NATIONALLICENCE 700 1- Liu Yan 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 aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/8(2015-08-01), 1-12 1610-2940 21:8<1 2015 21 894