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Extensive ab initio study of the electronic states of S 2 molecule including spin-orbit coupling

机译：S 2分子电子态的广泛从头算研究，包括自旋轨道耦合

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摘要

The potential energy curves (PECs) of 15 Λ-S states and 24 Ω states generated from the 13 Λ-S bound states of the S2 molecule are investigated in detail using an ab initio quantum chemical method. The PECs are calculated for internuclear separations from 0.12 to 1.10 nm by the complete active space self-consistent field method, which is followed by the internally contracted multireference configuration interaction approach with the Davidson modification (MRCI + Q). The spin-orbit (SO) coupling effect is accounted for by the Breit-Pauli Hamiltonian. To discuss the effect on the energy splitting by the core-electron correlations, the all-electron basis set, cc-pCVTZ with and without 2s2p correlations, is used for the SO coupling calculations of the A_3 and B′3Πg Λ-S states since their measurements can be found in the literature. By comparison, the cc-pCVTZ basis set with 2s2p correlations is chosen for the SO coupling calculations of 13 Λ-S bound states. To improve the quality of PECs, core-valence correlation and scalar relativistic corrections are included. Scalar relativistic correction calculations are made using the third-order Douglas-Kroll Hamiltonian (DKH3) approximation at the level of a cc-pV5Z basis set. Core-valence correlation corrections are taken into account with a cc-pCVTZ basis set. The spectroscopic parameters of 13 Λ-S bound states and 24 Ω states are calculated. With the PECs obtained by the MRCI + Q/aug-cc-pV6Z + CV + DK + SO calculations, the SO coupling splitting energies are 379.25 cm~(-1) between the A′3 and A′2 Ω state, 83.40 cm~(-1) between the A1 and A0- Ω state and 210.91 cm~(-1) between the B′2 and B′1 Ω state, which agree well with the corresponding measurements of 383, 77.51 and 209 cm~(-1), respectively. Moreover, other spectroscopic parameters are also in excellent agreement with the measurements. It demonstrates that the spectroscopic parameters of 24 Ω states reported here for the first time can be expected to be reliable predicted ones.
机译：使用从头算量子化学方法详细研究了由S2分子的13个Λ-S键合态生成的15个Λ-S态和24Ω态的势能曲线（PEC）。通过完整的有源空间自洽场方法计算PEC的0.12 nm至1.10 nm的核间距，然后通过内部收缩的多参考构型相互作用方法进行戴维森修正（MRCI + Q）。 Breit-Pauli Hamiltonian解释了自旋轨道（SO）耦合效应。为了讨论芯电子相关对能量分裂的影响，将具有和不具有2s2p相关的全电子基集cc-pCVTZ用于A_3和B′3ΠgΛ-S状态的SO耦合计算。它们的测量值可以在文献中找到。相比之下，选择具有2s2p相关性的cc-pCVTZ基集进行13个Λ-S束缚态的SO耦合计算。为了提高PEC的质量，包括了核心价相关性和标量相对论校正。标量相对论校正计算是使用cc-pV5Z基集级别的三阶Douglas-Kroll Hamiltonian（DKH3）近似值进行的。 cc-pCVTZ基集考虑了核心价相关校正。计算了13个Λ-S束缚态和24Ω态的光谱参数。通过MRCI + Q / aug-cc-pV6Z + CV + DK + SO计算得到的PECs，A'3和A'2Ω状态之间的SO耦合分裂能为379.25 cm〜（-1），为83.40 cm A1和A0-Ω状态之间的〜（-1）和B'2和B'1Ω状态之间的210.91 cm〜（-1），与383、77.51和209 cm〜（- 1）。此外，其他光谱参数也与测量值非常吻合。结果表明，这里首次报道的24Ω状态的光谱参数可以预期是可靠的预测参数。

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