De Vos John, Schröder Benjamin, Rauhut Guntram
Institute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany; Department of Chemistry, Ghent University, Krijgslaan 281, 9000, Ghent, Belgium.
Institute for Physical Chemistry, University of Göttingen, Tammannstr. 6, 37077, Göttingen, Germany.
Spectrochim Acta A Mol Biomol Spectrosc. 2023 Dec 5;302:123083. doi: 10.1016/j.saa.2023.123083. Epub 2023 Jul 1.
The (ro)vibrational spectra of thiirane, c-CHS, and its fully deuterated isotopologue, c-CDS, have been studied by means of vibrational configuration interaction theory, VCI, its incremental variant, iVCI, and subsequent variational rovibrational calculations, RVCI, which rely on multidimensional potential energy surfaces of coupled-cluster quality including up to four-mode coupling terms. Accurate geometrical parameters, fundamental vibrational transitions and first overtones, rovibrational spectra and rotational spectroscopic constants have been determined from these calculations and were compared with experimental results whenever available. A number of tentative misassignments in the vibrational spectra could be resolved and most results for the deuterated thiirane are high-level predictions, which may guide experiments to come. Besides this, a new implementation of infrared intensities within the iVCI framework has been tested for the transitions of the title compounds and are compared with results obtained from standard VCI calculations.
利用振动组态相互作用理论（VCI）、其增量变体（iVCI）以及随后的变分振转计算（RVCI），对环硫乙烷（c-CHS）及其全氘代同位素分子（c-CDS）的（振）转光谱进行了研究。RVCI计算依赖于耦合簇质量的多维势能面，其中包括高达四模耦合项。通过这些计算确定了精确的几何参数、基本振动跃迁和第一泛音、振转光谱以及转动光谱常数，并在有实验结果时与实验结果进行了比较。振动光谱中一些初步的错误归属得以解决，并且对于氘代环硫乙烷的大多数结果都是高水平预测，这可能会为未来的实验提供指导。除此之外，在iVCI框架内对红外强度的一种新实现方法针对标题化合物的跃迁进行了测试，并与从标准VCI计算获得的结果进行了比较。
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