Correlation of the Charge Resonance Interaction with Cluster Conformations Probed by Electronic Spectroscopy of Dimer Radical Cations of CO2 and CS2 in a Cryogenic Ion Trap

Koyama Masahiro

Muramatsu Satoru

Hirokawa Yasuaki

Iriguchi Jidai

Matsuyama Akihito

Inokuchi Yoshiya

The Journal of Physical Chemistry Letters

Radical cations of dimeric clusters of carbon dioxide/disulfide, [(CX2)2]+• (X = O and S), form strong intracluster bonds through charge resonance (CR) interactions. We herein performed electronic photodissociation spectroscopy of [(CX2)2]+• while regulating the temperature under ambient and cryogenic conditions using a quadrupole ion trap. Both ions exhibited broad band absorption in the near-infrared–visible light region; it is called the “CR band”, as a measure of the strength of the CR interaction. Strikingly, this band underwent a noticeable blue shift upon cryogenic cooling for [(CS2)2]+• while not for [(CO2)2]+•. On the basis of quantum chemical calculations with a coupled cluster method, the band shift was attributed to the variations in the relative population of two energetically close conformers found for [(CS2)2]+•. This study highlights a strong correlation between CR interactions and conformation of the radical dimer cations, demonstrating the exceptional significance of cryogenic cooling in the chemistry of ionic molecular clusters.

eng

American Chemical Society

This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpclett.3c03500

This is not the published version. Please cite only the published version.

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[DOI] https://doi.org/10.1021/acs.jpclett.3c03500 isVersionOf

日本学術振興会

Japan Society for the Promotion of Science

[Crossref Funder] https://doi.org/10.13039/501100001691

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日本学術振興会

Japan Society for the Promotion of Science

[Crossref Funder] https://doi.org/10.13039/501100001691

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