Ab initio UHF/6-31G** method has been employed to study the mechanism of the thermal isomerization from 1,2-butadiene to 1,3-butadiene. The energies were corrected at MP2//6-31G**+ZPE(zero-point energy) level. The res...Ab initio UHF/6-31G** method has been employed to study the mechanism of the thermal isomerization from 1,2-butadiene to 1,3-butadiene. The energies were corrected at MP2//6-31G**+ZPE(zero-point energy) level. The results indicate that it is a stepwise reaction via a radical intermediate. The calculated activation barriers are 65.01 and 64.16 kcal./mol., respectively.展开更多
RECENTLY much attention has been paid to the mechanism of the dissociation of furancations.The reason is not only that some neutral molecules by ultraviolet（UV）light mayproduce C<sub>4</sub>H<sub>4...RECENTLY much attention has been paid to the mechanism of the dissociation of furancations.The reason is not only that some neutral molecules by ultraviolet（UV）light mayproduce C<sub>4</sub>H<sub>4</sub>O<sup>+</sup>,but also that the investigation of this mechanism can help us understand展开更多
The microcanonical rate constants for the hydrogen-transfer process of HCCF (reaction 7) and the fluoro-transfer process of FCCF (reaction 8) are carried out with tunneling correction and curvature correction. The res...The microcanonical rate constants for the hydrogen-transfer process of HCCF (reaction 7) and the fluoro-transfer process of FCCF (reaction 8) are carried out with tunneling correction and curvature correction. The results show that the tunneling effects and curvature effects on the rate constant of reaction 7 is quite different from that of reaction 8. The rate constants for different rotational states are also studied for these reactions.展开更多
文摘Ab initio UHF/6-31G** method has been employed to study the mechanism of the thermal isomerization from 1,2-butadiene to 1,3-butadiene. The energies were corrected at MP2//6-31G**+ZPE(zero-point energy) level. The results indicate that it is a stepwise reaction via a radical intermediate. The calculated activation barriers are 65.01 and 64.16 kcal./mol., respectively.
文摘RECENTLY much attention has been paid to the mechanism of the dissociation of furancations.The reason is not only that some neutral molecules by ultraviolet（UV）light mayproduce C<sub>4</sub>H<sub>4</sub>O<sup>+</sup>,but also that the investigation of this mechanism can help us understand
基金Project supported by the State Science and Technology Commission of China.
文摘The microcanonical rate constants for the hydrogen-transfer process of HCCF (reaction 7) and the fluoro-transfer process of FCCF (reaction 8) are carried out with tunneling correction and curvature correction. The results show that the tunneling effects and curvature effects on the rate constant of reaction 7 is quite different from that of reaction 8. The rate constants for different rotational states are also studied for these reactions.
