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On the alternating structure of cyclo[18]carbon

Zhang, Jing-Xuan and Yang, Junjie and Sheong, Fu Kit (2022) On the alternating structure of cyclo[18]carbon. . (Unpublished) https://resolver.caltech.edu/CaltechAUTHORS:20220414-26135000

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Abstract

Cyclo[18]carbon, has been recently characterized by high-resolution atomic force microscopy which revealed a polyynic structure with alternating single and triple bonds. It is natural to ask why it does not exhibit bond equalization and adopt a cumulenic structure. This paper, on the other hand, begins with the opposite question: why we expect it to exhibit bond equalization in the first place. We then reexamine whether these intuitive arguments are theoretically sound. Hückel model, which was often attributed as the underlying reason for the famous 4N+2 electron-counting rule for aromatics, was reviewed with minimal structural flexibility introduced, which surprisingly revealed that even benzene would undergo bond alternation under the Hückel framework. This analysis is confirmed by extended Hückel calculations. DFT and semi-empirical calculations revealed that internuclear repulsion would be necessary for a model to correctly predict the D6h structure of benzene. Similar scenario was observed for C18, except that a greater fraction of exact exchange may result in a small energy gain when molecule distorts from D18h to D9h geometry. HOMO energy lowering and LUMO energy rising were found in the symmetry-lowering distortion of both benzene and C18, thus disqualifying the usual explanation of the bond alternating structure of C18 based on second-order Jahn-Teller effect. Finally, a hydrogen-ring model was presented as a toy model to investigate the origin of bond equalization of so-called aromatic systems, which clearly revealed the role of nuclear repulsion in favoring high-symmetry structure while electronic energy monotonically decreases in symmetry-lowering process.


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
https://doi.org/10.26434/chemrxiv-2022-sgq6fDOIDiscussion Paper
ORCID:
AuthorORCID
Zhang, Jing-Xuan0000-0002-1358-2789
Additional Information:The content is available under CC BY NC ND 4.0 License. The author(s) have declared they have no conflict of interest with regard to this content. The author(s) have declared ethics committee/IRB approval is not relevant to this content.
Subject Keywords:cyclo[18]carbon; bond equalization; symmetry breaking; aromaticity; Huckel model
DOI:10.26434/chemrxiv-2022-sgq6f
Record Number:CaltechAUTHORS:20220414-26135000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220414-26135000
Official Citation:Zhang J-X, Yang J, Sheong FK. On the alternating structure of cyclo[18]carbon. ChemRxiv. 2022. doi:10.26434/chemrxiv-2022-sgq6f
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114299
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:19 Apr 2022 22:23
Last Modified:19 Apr 2022 22:23

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