Zou Wenli, Liu Wenjian
Institute of Theoretical and Computational Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, People's Republic of China.
J Chem Phys. 2006 Apr 21;124(15):154312. doi: 10.1063/1.2187000.
The low-lying electronic states of the nickel monohalides, i.e., NiF, NiCl, NiBr, and NiI, are investigated by using multireference second-order perturbation theory with relativistic effects taken into account. For the energetically lowest 11 lambda-S states and 26 omega states there into, the potential energy curves and corresponding spectroscopic constants (vertical and adiabatic excitation energies, equilibrium bond lengths, vibrational frequencies, and rotational constants) are reported. The calculated results are grossly in very good agreement with those solid experimental data. In particular, the ground state of NiI is shown to be different from those of NiF, NiCl, and NiBr, being in line with the recent experimental observation. Detailed analyses are provided on those states that either have not been assigned or have been incorrectly assigned by previous experiments.
利用考虑相对论效应的多参考二阶微扰理论，对一卤化镍（即NiF、NiCl、NiBr和NiI）的低电子态进行了研究。对于其中能量最低的11个λ-S态和26个ω态，报道了势能曲线及相应的光谱常数（垂直和绝热激发能、平衡键长、振动频率和转动常数）。计算结果与那些可靠的实验数据总体上非常吻合。特别是，NiI的基态与NiF、NiCl和NiBr的基态不同，这与最近的实验观测结果一致。对那些以前的实验未归属或归属错误的态进行了详细分析。
