Theoretical study of the C(3P) + trans-C4H8 reaction.
The complex triplet potential energy surface for the reaction of ground-state carbon atom C((3)P) with trans-C(4)H(8) is theoretically investigated at the B3LYP/6-311G(d,p) and G3B3(single-point) levels. Various possible isomerization and dissociation pathways are probed. The initial association between C((3)P) and trans-C(4)H(8) is found to be the C((3)P) addition to the C=C bond of trans-C(4)H(8) to barrierlessly generate the three-membered cyclic isomer 1 CH(3)-cCHCCH-CH(3). Subsequently, 1 undergoes a ring-opening process to form the chainlike isomer 3a cis-trans-CH(3)CHCCHCH(3), which can either lead to P(6)((2)CH(3)CHCCCH(3) + (2)H) via the C-H bond cleavage or to P(7)((2)CH(3)CHCCH + (2)CH(3)) via C-C bond rupture. These two paths are the most favorable channels of the title reaction. Other channels leading to products P(1)((2)CH(3)-cCHCCH + (2)CH(3)), P(2)((2)CH(3)-cCHCC-CH(3) + (2)H), P(3)(trans-(2)CH(3)CHCH + (2)C(2)H(3)), P(4)(cis-(2)CH(3)CHCH + (2)C(2)H(3)), P(5)((3)CH(3)CH + (1)CH(3)CCH), P(8)(cis-(2)CH(3)CHCHCCH(2) + (2)H), P(9)(trans-(2)CH(3)CHCHCCH(2) + (2)H), P(10)((2)CH(3)CCCH(2) + (2)CH(3)), and P(11)((2)CH(3)CHCCHCH(2) + (2)H), however, are much less competitive due to either kinetic or thermodynamic factors. Because the intermediates and transition states involved in the C((3)P) + trans-C(4)H(8) reaction all lie below the reactant, the title reaction is expected to be rapid, as is consistent with the measured large rate constant. Our results may be helpful for future experimental investigation of the title reaction.
Li
Yan
Y
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
Liu
Hui-ling
HL
Huang
Xu-ri
XR
Wang
De-Quan
DQ
Sun
Chia-chung
CC