caa a22 4500 605488150 CHVBK 20210128100454.0 cr unu---uuuuu 210128e20150801xx s 000 0 eng 10.1007/s00214-015-1699-2 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1699-2 Direct dynamics study on hydrogen abstraction reaction of morpholine with hydroxyl radical [Elektronische Daten] [Hong Gao, Miaomiao Wang, Tongyin Jin, Jian Shi, Xiaojun Yao, Nengzhi Jin] A dual-level direct dynamic study has been employed to investigate the H-abstraction reaction of morpholine (C4H9NO) with OH. The chair conformer of C4H9NO molecule is performed as the reactant because of the lower energy. The potential energy surfaces are obtained at the MC-QCISD/3//M06-2X/6-311+G(d, p) level. The rate constants are estimated using the improved canonical variational transition state theory with the small-curvature tunneling correction over a wide temperature range of 200 to 1000K, and a fitted four-parameter rate constant expression is obtained. The calculated rate constants are in good agreement with the available experimental values, and the negative temperature dependence of rate constant is found within 200-600K. Moreover, the contribution of each reaction site to the title reaction is discussed with respect to the temperature. The result shows that the H-abstraction reaction mainly takes place at the -CH2 group attached to the N atom at low temperatures, while as the temperature increases the contribution of the H-abstraction to the title reaction from the -NH group becomes larger rapidly, and the -NH group turns into the most important H-abstraction reaction site when the temperature is higher than 800K. Springer-Verlag Berlin Heidelberg, 2015 Morpholine nationallicence Rate constants nationallicence Variational transition state theory nationallicence Direct dynamics nationallicence Density functional theory nationallicence Gao Hong Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, People's Republic of China aut Wang Miaomiao Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, People's Republic of China aut Jin Tongyin Department of Chemistry, Hebei Normal University for Nationalities, 067000, Chengde, People's Republic of China aut Shi Jian Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, People's Republic of China aut Yao Xiaojun Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, People's Republic of China aut Jin Nengzhi Gansu Computing Center of China, 730000, Lanzhou, People's Republic of China aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/8(2015-08-01), 1-10 1432-881X 134:8<1 2015 134 214 https://doi.org/10.1007/s00214-015-1699-2 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/s00214-015-1699-2 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Gao Hong Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, People's Republic of China aut NATIONALLICENCE 700 1- Wang Miaomiao Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, People's Republic of China aut NATIONALLICENCE 700 1- Jin Tongyin Department of Chemistry, Hebei Normal University for Nationalities, 067000, Chengde, People's Republic of China aut NATIONALLICENCE 700 1- Shi Jian Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, People's Republic of China aut NATIONALLICENCE 700 1- Yao Xiaojun Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province and College of Chemistry and Chemical Engineering, Lanzhou University, 730000, Lanzhou, People's Republic of China aut NATIONALLICENCE 700 1- Jin Nengzhi Gansu Computing Center of China, 730000, Lanzhou, People's Republic of China aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/8(2015-08-01), 1-10 1432-881X 134:8<1 2015 134 214