Accurate spectroscopic constants of the lowest three electronic states in halonitrenes with multireference configuration interaction

作者：Shan, Shimin; Yin, Shuang; Lian, Yi; Xu, Haifeng^*; Yan, Bing^*

来源：International Journal of Quantum Chemistry, 2018, 118(16): e25649.

DOI：10.1002/qua.25649

• core-valence correlation
• icMRCI plus Q
• nitrenes
• scalar relativistic effect
• spectroscopic constants
• spin-orbit coupling effect

Internally contracted multireference configuration interaction (icMRCI) calculations of the ground state (X-3 sigma(-)), the first excited state (a(1)) as well as the second excited state (b(1)sigma(+)) have been performed for a series of halogenated nitrenes NXs (X=Cl, Br, and I). Accurate spectroscopic constants of these lowest three electronic states of each NX were obtained in this work using MRCI methods with aug-cc-pVXZ (X=T, Q, 5) basis sets and complete basis set (CBS) limit. In addition, various corrections, including the Davidson correction, scalar relativistic effect, core-valence correlation, and spin-orbit coupling effect, have been studied in calculating spectroscopic constants, especially for heavy-atom nitrenes. Comparisons have been made with previous computational and experimental results where available. The icMRCI+Q calculations presented in this work provide a comprehensive series of results at a consistent high level of theory for all of the halogenated nitrenes.

• 出版日期2018-8-15
• 单位吉林大学