Photoelectron spectra of infinitenes and topoisomers

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2024-03-13 DOI:10.1016/j.elspec.2024.147431

Igor Novak

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引用次数: 0

Abstract

The vertical, valence ionization energies of some [12]circulenes (C₄₈H₂₄) topoisomers have been calculated as free molecules in the gas phase using high-level ab initio coupled-cluster method: EOM-DLPNO-CCSD. Their valence electronic structures depend on molecular topology. We have used calculated vertical, valence ionization energies to simulate their UV photoelectron spectra (UPS). HOMO-LUMO bandgaps and the influence of molecular topology on the spectra were also studied. Our results indicate the presence and importance of stabilizing intramolecular π-π stacking interactions and molecular distortion (via strain energy) on electronic structures and UPS spectra. For example, the HOMO ionization energy increases along the sequence: infinitene<Möbius<Kekulene. The results presented may help in identification and analysis of photoelectron spectra of circulenes which can not be obtained in the gas phase, but rather as adsorbed molecules on metal surface.

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无穷乙烯和拓扑异构体的光电子能谱

采用高水平 ab initio 耦合簇方法计算了一些 [12] 环烯（C48H24）拓扑异构体在气相中作为自由分子的垂直价电离能：EOM-DLPNO-CCSD。它们的价电子结构取决于分子拓扑结构。我们利用计算出的垂直价电离能模拟了它们的紫外光电子能谱（UPS）。我们还研究了 HOMO-LUMO 带隙以及分子拓扑结构对光谱的影响。我们的研究结果表明，稳定分子内 π-π 堆叠相互作用和分子变形（通过应变能）对电子结构和 UPS 光谱有重要影响。例如，HOMO 电离能沿着以下序列增加：无限烯<莫比乌斯<凯库烯。这些结果有助于识别和分析环烯的光电子能谱，因为环烯不能在气相中获得，而是作为吸附分子吸附在金属表面上。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.