Internal rotation barrier and transition state for glyoxal
Internal rotation barrier and transition state for glyoxal
复制标题
乙二醛的内旋转势垒和过渡态
DOI：
10.1063/1.441646
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发表时间：
1981
影响因子：
4.4
通讯作者：
H. Schaefer
中科院分区：
文献类型：
--
作者：
Y. Osamura;H. Schaefer
对顺式和反式乙二醛的电子基态以及连接它们的过渡态进行了完整的结构优化。自洽场（SCF）理论与梯度技术和双zeta +极化基集的收缩高斯函数相结合。构型相互作用研究证实了相关效应相对不重要的观点。反式构象比顺式异构体低5.86千卡。从顺式方向看，旋转势垒仅为0.94 kcal.这些结果和预测的电离势结合最近的实验进行了讨论。最后，对乙二醛光解反应的机理进行了评述。
Complete structural optimizations have been carried out for the electronic ground states of cis‐ and trans‐glyoxal and for the transition state connecting them. Self‐consistent‐field (SCF) theory was used in conjunction with gradient techniques and a double zeta plus polarization basis set of contracted Gaussian functions. Configuration interaction studies confirm the view that correlation effects are relatively unimportant in the treatment of this rotational barrier. The trans conformation is predicted to lie 5.86 kcal below the cis isomer. From the cis side, the barrier to rotation is only 0.94 kcal. These results and the predicted ionization potentials are discussed in light of recent experiments. Finally, some mechanistic comments on the photodissociation of glyoxal are presented.