caa a22 4500 605487189 CHVBK 20210128100449.0 cr unu---uuuuu 210128e20150101xx s 000 0 eng 10.1007/s00214-014-1599-x doi (NATIONALLICENCE)springer-10.1007/s00214-014-1599-x Theoretical and kinetic study of reaction C2H+C3H6 on the C5H7 potential energy surface [Elektronische Daten] [Chun-Ming Gong, Hong-Bo Ning, Ze-Rong Li, Xiang-Yuan Li] The reaction mechanisms for reaction C2H+C3H6 (propene) on the C5H7 potential energy surface (PES) have been investigated by using quantum chemical calculations combined with canonical transition state theory and Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) theory. The optimization of the geometries and the calculation of the vibrational frequencies of reactants, transition states, and products are performed at the B3LYP/CBSB7 level of theory. The composite CBS-QB3 method is applied for energy calculations. The rate constants for reactions with tight transition states are obtained by canonical transition state theory, while the rate constants for barrierless reactions at the high-pressure limit are determined by the variational transition state theory. The rate constants for pressure-dependent reactions are obtained by RRKM/ME theory. The reaction of C2H+C3H6 is initiated by the internal and terminal additions of C2H to C3H6 without an entrance barrier, and the adduct of the internal and terminal additions is 2-methyl-1-butyl-3-yne (C5H7) and 4-pentyl-1-yne (C5H7), respectively. Products vinylacetylene (C4H4)+CH3 and 2-methyl-1-buten-3-yne (C5H6)+H are favored by the internal C2H addition to C3H6, whereas products 3-penten-1-yne (C5H6)+H and 4-penten-1-yne (C5H6)+H are preferred for the terminal C2H addition. The calculated rate constants are in good agreement with those available from the literature, and they are also given in modified Arrhenius equation form, which are useful in combustion modeling of hydrocarbons. Springer-Verlag Berlin Heidelberg, 2014 C5H7 PES nationallicence Mechanism nationallicence Rate constant nationallicence Thermochemical properties nationallicence Branching ratio nationallicence Gong Chun-Ming College of Chemical Engineering, Sichuan University, 610065, Chengdu, People's Republic of China aut Ning Hong-Bo College of Chemical Engineering, Sichuan University, 610065, Chengdu, People's Republic of China aut Li Ze-Rong College of Chemistry, Sichuan University, 610064, Chengdu, People's Republic of China aut Li Xiang-Yuan College of Chemical Engineering, Sichuan University, 610065, Chengdu, People's Republic of China aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/1(2015-01-01), 1-14 1432-881X 134:1<1 2015 134 214 https://doi.org/10.1007/s00214-014-1599-x 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/s00214-014-1599-x text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Gong Chun-Ming College of Chemical Engineering, Sichuan University, 610065, Chengdu, People's Republic of China aut NATIONALLICENCE 700 1- Ning Hong-Bo College of Chemical Engineering, Sichuan University, 610065, Chengdu, People's Republic of China aut NATIONALLICENCE 700 1- Li Ze-Rong College of Chemistry, Sichuan University, 610064, Chengdu, People's Republic of China aut NATIONALLICENCE 700 1- Li Xiang-Yuan College of Chemical Engineering, Sichuan University, 610065, Chengdu, People's Republic of China aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/1(2015-01-01), 1-14 1432-881X 134:1<1 2015 134 214