Ab initio calculation on the low-lying excited states of Si-2(+) cation including spin-orbit coupling

作者：Liu, Yanlei; Zhai, Hongsheng; Zhang, Xiaomei; Liu, Yufang^*

来源：Chemical Physics, 2013, 425: 156-161.

DOI：10.1016/j.chemphys.2013.09.002

• MRCI( plus Q)
• Spin-orbit coupling effect
• Potential energy curve
• Spectroscopic constants

Ab initio all-electron relativistic calculations of the low-lying excited states of Si-2(+) have been performed at MRCI+Q/AVQZ level. The calculated electronic states, including 12 doublet and 12 quartet Lambda-S states, are correlated to the dissociation limit of Si((3)Pg) + Si+(Pu-2). Spin-orbit interaction is taken into account via the state interaction approach with the full Breit-Pauli Hamiltonian, which causes the entire 24 Lambda-S states to split into 54 Omega states. This is the first time that spin-orbit coupling (SOC) calculation has been performed on Si-2(+). The obtained potential energy curves (PECs) of Lambda-S and Omega states are respectively depicted with the aid of the avoided crossing rule between the same symmetry. The spectroscopic constants of the bound Lambda-S and Omega states are determined, and excellent agreements with the latest theoretical results are achieved.

• 出版日期2013-11-8
• 单位河南师范大学