Shan Shimin, Yan Peiyuan, Zhang Xiaomei, Yin Shuang, Yuan Xiang, Xu Haifeng, Yan Bing
Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012, China.
Phys Chem Chem Phys. 2017 Jul 21;19(27):17735-17744. doi: 10.1039/c7cp02575k. Epub 2017 Jun 28.
We present herein a high-level ab initio study on the mono-iodine substituted carbene, CHI, using internally contracted multireference configuration interaction (icMRCI-F12) with Davidson correction which employs wave functions that explicitly depend on the electron-electron distance. The spin-orbit coupling (SOC) effect was included in our calculations. A total of 20 spin-free states with vertical transition energy up to 7.4 eV, as well as 50 spin-coupled states generated from the spin-free states via the SOC were studied. The results show significant influence of the SOC on the bond angles and the harmonic vibrational frequencies of the bending mode of the ground state (XA') and the lowest triplet state (aA''). Potential energy curves along the bond angle and the bond lengths of the electronic excited states of CHI were investigated. Based on our calculations, photodissociation dynamics in the ultraviolet region was disscussed for the first time, which would pave the way to further experimental investigations of CHI.
我们在此展示了一项关于单碘取代卡宾CHI的高水平从头算研究，采用了具有戴维森校正的内收缩多参考组态相互作用（icMRCI-F12）方法，该方法所使用的波函数明确依赖于电子 - 电子距离。我们的计算中包含了自旋 - 轨道耦合（SOC）效应。研究了总共20个垂直跃迁能量高达7.4 eV的无自旋态，以及通过SOC从无自旋态产生的50个自旋耦合态。结果表明，SOC对基态（XA'）和最低三重态（aA''）的键角以及弯曲模式的谐振动频率有显著影响。研究了CHI电子激发态沿键角和键长的势能曲线。基于我们的计算，首次讨论了紫外区域的光解离动力学，这将为CHI的进一步实验研究铺平道路。
