Composite vibrational spectroscopy of the group 12 difluorides: ZnF2, CdF2, and HgF2,The Journal of Chemical Physics

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Composite vibrational spectroscopy of the group 12 difluorides: ZnF2, CdF2, and HgF2
The Journal of Chemical Physics ( IF 3.1 ) Pub Date : 2016-04-11 14:26:59 , DOI: 10.1063/1.4945449
Victor G. Solomonik ₁ , Alexander N. Smirnov ₁ , Ilya S. Navarkin ₁

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The vibrational spectra of group 12 difluorides, MF₂ (M = Zn, Cd, Hg), were investigated via coupled cluster singles, doubles, and perturbative triples, CCSD(T), including core correlation, with a series of correlation consistent basis sets ranging in size from triple-zeta through quintuple-zeta quality, which were then extrapolated to the complete basis set (CBS) limit using a variety of extrapolation procedures. The explicitly correlated coupled cluster method, CCSD(T)-F12b, was employed as well. Although exhibiting quite different convergence behavior, the F12b method yielded the CBS limit estimates closely matching more computationally expensive conventional CBS extrapolations. The convergence with respect to basis set size was examined for the contributions entering into composite vibrational spectroscopy, including those from higher-order correlation accounted for through the CCSDT(Q) level of theory, second-order spin-orbit couplingeffects assessed within four-component and two-component relativistic formalisms, and vibrational anharmonicity evaluated via a perturbative treatment. Overall, the composite results are in excellent agreement with available experimental values, except for the CdF₂ bond-stretching frequencies compared to spectral assignments proposed in a matrix isolation infrared and Raman study of cadmium difluoride vapor species [Loewenschuss et al., J. Chem. Phys. 50, 2502 (1969); Givan and Loewenschuss, J. Chem. Phys. 72, 3809 (1980)]. These assignments are called into question in the light of the composite results.

中文翻译：

第12组二氟化物的复合振动光谱法：ZnF2，CdF2和HgF2

第12组二氟化物MF ₂的振动光谱（M = Zn，Cd，Hg），是通过耦合的簇单，双和扰动三重态CCSD（T）进行研究的，包括核心相关性，以及一系列相关性一致的基础集，其大小范围从三重峰到五重峰。 zeta质量，然后使用各种外推程序将其外推到完整基集（CBS）极限。还使用了显式相关的耦合聚类方法CCSD（T）-F12b。尽管表现出完全不同的收敛行为，但F12b方法得出的CBS极限估计值与更昂贵的常规CBS外推法非常匹配。检验了相对于基集大小的收敛性，以了解复合振动光谱学中的贡献，包括通过CCSDT（Q）理论水平解释的高阶相关性，通过四分量和二分量相对论形式主义评估的二阶自旋轨道耦合效应以及通过微扰处理评估的振动非谐性。总体而言，除了CdF以外，综合结果与可用的实验值非常吻合与在基体隔离红外和拉曼研究中对二氟化镉蒸气物质提出的光谱分配相比，有_2种键拉伸频率[Loewenschuss等。，J. Chem。物理 50，2502（1969）; Givan和Loewenschuss，《化学》杂志。物理 72，3809（1980）]。鉴于综合结果，这些分配受到质疑。

更新日期：2016-04-12

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