Author/Authors :
Qu، نويسنده , , Zheng-wang and Zhu، نويسنده , , Hui and Zhang، نويسنده , , Xiao-dong and Ai، نويسنده , , Xi Cheng and Zhang، نويسنده , , Jian-ping and Zhang، نويسنده , , Xing-kang and Zhang، نويسنده , , Qi-yuan، نويسنده ,
Abstract :
The cycloreversion of cyclobutane radical cation (1 c-C4H8+) has been investigated in detail at the UB3LYP/6-31++G(d,p) level of theory. The `rotatingʹ mechanism of cycloreversion via the `tightly boundʹ intermediate of tetramethylene radical cation (2 CH2CH2CH2CH2+) has been revealed for the first time. It is shown that both the present `rotatingʹ mechanism and the previous `shiftingʹ one via the `loosely boundʹ complex (3 C2H4·C2H4+) may compete intensively with each other for this reaction, leading to the low-lying isomers (4 c-CH2CH2CH–CH3+ and 5 CH3CH2CHCH2+) in low temperature but to the dissociation products 6 C2H4+C2H4+ in high temperature above 600 K.
