Accurate potential energy curves and spectroscopic properties of the 27 Λ-S states and 73 Ω states of the PO radical
Accurate potential energy curves and spectroscopic properties of the 27 Λ-S states and 73 Ω states of the PO radical
复制标题
PO自由基27个Λ-S态和73Ω态的准确势能曲线和光谱特性
DOI：
--
复制
发表时间：
2017
期刊：
影响因子：
--
通讯作者：
Zun
中科院分区：
文献类型：
--
作者：
Hui Liu;D. Shi;Jinfeng Sun;Zun
摘要计算了PO自由基的27个Λ-S态和73个Ω态的势能曲线。计算是使用CASSCF方法，其次是内部收缩多参考组态相互作用（icMRCI）的方法。为了提高佩奇的质量，除了Davidson修正外，还加入了核价相关和标量相对论修正。在27个Λ-S态中，16个Λ +态在任何情况下都是排斥的。14个Φ态和16个Π态是束缚态，但由于自旋轨道耦合（SOC）效应，它们变成排斥态。考虑到SOC效应，对34个电子态进行了反转，得到了34个电子态，包括α 4 Π、C′2Δ、D′2Π、14Δ、12Φ、16 π +和16 π。F2+态具有双威尔斯孔。在B2 π +和F2 π +态、F2 π +和32 π +态、C′2Δ和22Δ态、14Δ和24Δ态、24Δ和34 Δ态、24 π和34 π态以及34Π和44Π态之间存在避免的交叉。c4 <$+、24 <$+、34 <$+、34 <$、44 <$、54 <$、34Δ、14Φ和16 <$态是弱束缚态，阱深在几百cm−1以内。推导了光谱参数。评价了SOC对光谱性质的影响。在这里得到的光谱结果可以预期是可靠的预测。
ABSTRACT The potential energy curves (PECs) were calculated for the 27 Λ-S states and 73 Ω states of PO radical. The calculations were done using the CASSCF method, which was followed by the internally contracted multireference configuration interaction (icMRCI) approach. To improve the quality of PECs, core-valence correlation and scalar relativistic corrections as well as Davidson correction were included. Of the 27 Λ-S states, the 16Σ+ state was repulsive at any case. The 14Φ and 16Π states were bound, but they became repulsive with the spin-orbit coupling (SOC) effect accounted for. The 34Σ+, a4Π, C′2Δ, D′2Π, 14Δ, 12Φ, 16Σ+ and 16Π states were inverted with the SOC effect included. The F2Σ+ state had double wells. The avoided crossings existed between the B2Σ+ and F2Σ+ states, the F2Σ+ and 32Σ+ states, the C′2Δ and 22Δ states, the 14Δ and 24Δ states, the 24Δ and 34Δ states, the 24Π and 34Π states and the 34Π and 44Π states. The c4Σ+, 24Σ+, 34Σ+, 34Π, 44Π, 54Π, 34Δ, 14Φ and 16Π states were weakly bound, which well depths were within several hundred cm−1. The spectroscopic parameters were derived. The SOC effect on the spectroscopic properties was evaluated. The spectroscopic results obtained here could be expected to be reliably predicted ones.