{"title":"合成硫代苯甲酸的微波光谱与取代结构","authors":"Aaron J. Reynolds, Kenneth R. Leopold","doi":"10.1016/j.jms.2023.111787","DOIUrl":null,"url":null,"abstract":"<div><p>The rotational spectrum of the <em>syn</em> conformer of thiobenzoic acid (C<sub>6</sub>H<sub>5</sub>COSH) has been observed by Fourier transform microwave spectroscopy in a supersonic jet. Spectra of all singly-substituted isotopologues involving <sup>13</sup>C, as well as the <sup>18</sup>O, <sup>33</sup>S, <sup>34</sup>S, and −SD derivatives have also been recorded. The isotopic data have been used to derive structural parameters of the molecular frame. The results are compared with density functional theory calculations at theM06-2X/6-311++G(d,p) level and show excellent agreement. The molecule is planar at the equilibrium geometry, and calculations of the energy profile for out-of-plane torsion of the SH group are presented. The <em>anti</em> conformer was not observed, consistent with calculations which indicate that it lies 2.6 kcal/mol higher in energy than the <em>syn</em> form.</p></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"394 ","pages":"Article 111787"},"PeriodicalIF":1.4000,"publicationDate":"2023-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Microwave spectrum and substitution structure of syn thiobenzoic acid\",\"authors\":\"Aaron J. Reynolds, Kenneth R. Leopold\",\"doi\":\"10.1016/j.jms.2023.111787\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The rotational spectrum of the <em>syn</em> conformer of thiobenzoic acid (C<sub>6</sub>H<sub>5</sub>COSH) has been observed by Fourier transform microwave spectroscopy in a supersonic jet. Spectra of all singly-substituted isotopologues involving <sup>13</sup>C, as well as the <sup>18</sup>O, <sup>33</sup>S, <sup>34</sup>S, and −SD derivatives have also been recorded. The isotopic data have been used to derive structural parameters of the molecular frame. The results are compared with density functional theory calculations at theM06-2X/6-311++G(d,p) level and show excellent agreement. The molecule is planar at the equilibrium geometry, and calculations of the energy profile for out-of-plane torsion of the SH group are presented. The <em>anti</em> conformer was not observed, consistent with calculations which indicate that it lies 2.6 kcal/mol higher in energy than the <em>syn</em> form.</p></div>\",\"PeriodicalId\":16367,\"journal\":{\"name\":\"Journal of Molecular Spectroscopy\",\"volume\":\"394 \",\"pages\":\"Article 111787\"},\"PeriodicalIF\":1.4000,\"publicationDate\":\"2023-04-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Spectroscopy\",\"FirstCategoryId\":\"101\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0022285223000528\",\"RegionNum\":4,\"RegionCategory\":\"物理与天体物理\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Spectroscopy","FirstCategoryId":"101","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022285223000528","RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"PHYSICS, ATOMIC, MOLECULAR & CHEMICAL","Score":null,"Total":0}
Microwave spectrum and substitution structure of syn thiobenzoic acid
The rotational spectrum of the syn conformer of thiobenzoic acid (C6H5COSH) has been observed by Fourier transform microwave spectroscopy in a supersonic jet. Spectra of all singly-substituted isotopologues involving 13C, as well as the 18O, 33S, 34S, and −SD derivatives have also been recorded. The isotopic data have been used to derive structural parameters of the molecular frame. The results are compared with density functional theory calculations at theM06-2X/6-311++G(d,p) level and show excellent agreement. The molecule is planar at the equilibrium geometry, and calculations of the energy profile for out-of-plane torsion of the SH group are presented. The anti conformer was not observed, consistent with calculations which indicate that it lies 2.6 kcal/mol higher in energy than the syn form.
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.