二硼烷非谐振动频率和强度:实验与理论

IF 1.4 4区 物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Journal of Molecular Spectroscopy Pub Date : 2024-02-01 DOI:10.1016/j.jms.2024.111887
Aaron I. Strom , Ibrahim Muddasser , Guntram Rauhut , David T. Anderson
{"title":"二硼烷非谐振动频率和强度:实验与理论","authors":"Aaron I. Strom ,&nbsp;Ibrahim Muddasser ,&nbsp;Guntram Rauhut ,&nbsp;David T. Anderson","doi":"10.1016/j.jms.2024.111887","DOIUrl":null,"url":null,"abstract":"<div><p>The vibrational dynamics of diborane have been extensively studied both theoretically and experimentally ever since the bridge structure of diborane was established in the 1950s. Numerous infrared and several Raman spectroscopic studies have followed in the ensuing years at ever increasing levels of spectral resolution. In parallel, <em>ab initio</em> computations of the underlying potential energy surface have progressed as well as the methods to calculate the anharmonic vibration dynamics beyond the double harmonic approximation. Nevertheless, even 70 years after the bridge structure of diborane was established, there are still significant discrepancies between experiment and theory for the fundamental vibrational frequencies of diborane. In this work we use parahydrogen (pH<sub>2</sub>) matrix isolation infrared spectroscopy to characterize six fundamental vibrations of B<sub>2</sub>H<sub>6</sub> and B<sub>2</sub>D<sub>6</sub> and compare them with results from configuration-selective vibrational configuration interaction theory. The calculated frequencies and intensities are in very good agreement with the pH<sub>2</sub> matrix isolation spectra, even several combination bands are well reproduced. We believe that the reason discrepancies have existed for so long is related to the large amount of anharmonicity that is associated with the bridge BH stretching modes. However, the calculated frequencies and intensities reported here for the vibrational modes of all three boron isotopologues of B<sub>2</sub>H<sub>6</sub> and B<sub>2</sub>D<sub>6</sub> are within ± 2.00 cm<sup>−1</sup> and ± 1.44 cm<sup>−1</sup>, respectively, of the experimental frequencies and therefore a refined vibrational assignment of diborane has been achieved.</p></div>","PeriodicalId":16367,"journal":{"name":"Journal of Molecular Spectroscopy","volume":"400 ","pages":"Article 111887"},"PeriodicalIF":1.4000,"publicationDate":"2024-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Diborane anharmonic vibrational frequencies and Intensities: Experiment and theory\",\"authors\":\"Aaron I. Strom ,&nbsp;Ibrahim Muddasser ,&nbsp;Guntram Rauhut ,&nbsp;David T. Anderson\",\"doi\":\"10.1016/j.jms.2024.111887\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The vibrational dynamics of diborane have been extensively studied both theoretically and experimentally ever since the bridge structure of diborane was established in the 1950s. Numerous infrared and several Raman spectroscopic studies have followed in the ensuing years at ever increasing levels of spectral resolution. In parallel, <em>ab initio</em> computations of the underlying potential energy surface have progressed as well as the methods to calculate the anharmonic vibration dynamics beyond the double harmonic approximation. Nevertheless, even 70 years after the bridge structure of diborane was established, there are still significant discrepancies between experiment and theory for the fundamental vibrational frequencies of diborane. In this work we use parahydrogen (pH<sub>2</sub>) matrix isolation infrared spectroscopy to characterize six fundamental vibrations of B<sub>2</sub>H<sub>6</sub> and B<sub>2</sub>D<sub>6</sub> and compare them with results from configuration-selective vibrational configuration interaction theory. The calculated frequencies and intensities are in very good agreement with the pH<sub>2</sub> matrix isolation spectra, even several combination bands are well reproduced. We believe that the reason discrepancies have existed for so long is related to the large amount of anharmonicity that is associated with the bridge BH stretching modes. However, the calculated frequencies and intensities reported here for the vibrational modes of all three boron isotopologues of B<sub>2</sub>H<sub>6</sub> and B<sub>2</sub>D<sub>6</sub> are within ± 2.00 cm<sup>−1</sup> and ± 1.44 cm<sup>−1</sup>, respectively, of the experimental frequencies and therefore a refined vibrational assignment of diborane has been achieved.</p></div>\",\"PeriodicalId\":16367,\"journal\":{\"name\":\"Journal of Molecular Spectroscopy\",\"volume\":\"400 \",\"pages\":\"Article 111887\"},\"PeriodicalIF\":1.4000,\"publicationDate\":\"2024-02-01\",\"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/S0022285224000146\",\"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/S0022285224000146","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}
引用次数: 0

摘要

自 20 世纪 50 年代确定二硼烷的桥式结构以来,人们对其振动动力学进行了广泛的理论和实验研究。在随后的几年里,人们又以越来越高的光谱分辨率进行了大量的红外光谱研究和一些拉曼光谱研究。与此同时,底层势能面的非初始计算以及双谐波近似之外的非谐波振动动力学计算方法也取得了进展。然而,即使在二硼烷的桥式结构确定 70 年后,实验与理论在二硼烷的基本振动频率方面仍存在显著差异。在这项工作中,我们使用对氢 (pH2) 基质隔离红外光谱法表征了 B2H6 和 B2D6 的六次基振,并将其与构型选择性振动构型相互作用理论的结果进行了比较。计算出的频率和强度与 pH2 基质分离光谱非常吻合,甚至几个组合带也得到了很好的再现。我们认为,长期存在差异的原因与桥 BH 拉伸模式的大量非谐波有关。不过,本文报告的 B2H6 和 B2D6 所有三种硼同素异形体的振动模式的计算频率和强度分别在实验频率的 ± 2.00 cm-1 和 ± 1.44 cm-1 范围内,因此二硼烷的振动赋值已经得到完善。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

摘要图片

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
Diborane anharmonic vibrational frequencies and Intensities: Experiment and theory

The vibrational dynamics of diborane have been extensively studied both theoretically and experimentally ever since the bridge structure of diborane was established in the 1950s. Numerous infrared and several Raman spectroscopic studies have followed in the ensuing years at ever increasing levels of spectral resolution. In parallel, ab initio computations of the underlying potential energy surface have progressed as well as the methods to calculate the anharmonic vibration dynamics beyond the double harmonic approximation. Nevertheless, even 70 years after the bridge structure of diborane was established, there are still significant discrepancies between experiment and theory for the fundamental vibrational frequencies of diborane. In this work we use parahydrogen (pH2) matrix isolation infrared spectroscopy to characterize six fundamental vibrations of B2H6 and B2D6 and compare them with results from configuration-selective vibrational configuration interaction theory. The calculated frequencies and intensities are in very good agreement with the pH2 matrix isolation spectra, even several combination bands are well reproduced. We believe that the reason discrepancies have existed for so long is related to the large amount of anharmonicity that is associated with the bridge BH stretching modes. However, the calculated frequencies and intensities reported here for the vibrational modes of all three boron isotopologues of B2H6 and B2D6 are within ± 2.00 cm−1 and ± 1.44 cm−1, respectively, of the experimental frequencies and therefore a refined vibrational assignment of diborane has been achieved.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
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.
期刊最新文献
High resolution laser diode spectroscopy of the hot bands of C2HD in the first overtone region of C-H stretching Buffer-gas cooling of hydrogen cyanide quantified by cavity-ringdown spectroscopy Pure rotational spectroscopic measurements on the electronic ground states of Hafnium monosulfide and Thorium monosulfide in highly excited vibrational states Isotopic species, vibrational states and nuclear quadrupole splitting in CH2Cl2 from rotational spectroscopy at 8–18 GHz Editorial Board
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1