1-氯甲基-1-氟硅环戊烷的啁啾脉冲傅立叶变换微波谱

IF 1.4 4区 物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Journal of Molecular Spectroscopy Pub Date : 2023-05-01 DOI:10.1016/j.jms.2023.111793
Tiara Pulliam , Frank E. Marshall , Theodore Carrigan-Broda , Daniel V. Hickman , Gamil Guirgis , G.S. Grubbs II
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引用次数: 0

摘要

利用啁啾脉冲傅立叶变换微波技术,首次记录了1-氯甲基-1-氟硅环戊烷的微波光谱。量子化学计算表明,两种能量最低的构象是扭反式构象和间扭式构象,而间扭式构象先前被证明有两种不同的构象,间扭式+(能量较低)和间扭式-(能量较高)。光谱分析只提供了扭转构象的观测,35Cl和37Cl同位素分别有253和85个跃迁。观察到r -支、a-型和b-型转变。光谱符合沃森s -约简哈密顿量,由旋转常数、四次离心畸变常数和核四极耦合常数组成,其中包括非对角线核四极耦合常数的测定,χab。利用二阶矩对其结构进行了解释,发现其环状结构与其他已知的硅环戊烷相似。对χzz进行了分析,并与其他类似分子进行了比较。对间扭构象的已知量子化学能的研究表明,报道的B3LYP能量与观测到的微波结果不一致。
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The chirped pulse, Fourier transform microwave spectrum of 1-chloromethyl-1-fluorosilacyclopentane

The microwave spectrum of 1-chloromethyl-1-fluorosilacyclopentane has been recorded for the first time using the chirped pulse, Fourier transform microwave technique. Quantum chemical calculations show the two lowest energy conformers as being a twist-trans and a gauche form with the gauche form previously being shown as having two separate conformations, a gauche+ (lower in energy) and gauche- (higher in energy) form. Analysis of the spectrum provided the observation of the twist-trans conformer only, with 253 and 85 transitions being assigned to the 35Cl and 37Cl isotopologues, respectively. R-branch, a- and b-type transitions were observed. The spectrum was fit to a Watson S-reduced Hamiltonian and consisted of rotational constants, quartic centrifugal distortion constants, and nuclear quadrupole coupling constants, including the determination of the off-diagonal nuclear quadrupole coupling constant, χab. Interpretation of the structure was provided using second moments and is found to have a similar ring structure to other known silacyclopentanes. Analysis of the χzz has been carried out and compared to other similar molecules. An investigation of the known quantum chemical energies of the gauche conformer reveals that the reported B3LYP energies do not align with the observed microwave results.

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来源期刊
CiteScore
2.70
自引率
21.40%
发文量
94
审稿时长
29 days
期刊介绍: The Journal of Molecular Spectroscopy presents experimental and theoretical articles on all subjects relevant to molecular spectroscopy and its modern applications. An international medium for the publication of some of the most significant research in the field, the Journal of Molecular Spectroscopy is an invaluable resource for astrophysicists, chemists, physicists, engineers, and others involved in molecular spectroscopy research and practice.
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