Intramolecular hole-transfer in protonated anthracene

Excitation spectra of protonated and deuteronated anthracene are obtained by triple-resonance dissociation spectroscopy. Very cold cations, protonated/deuteronated exclusively at the 9-position, are generated from two-colour two-photon threshold ionisation of 9-dihydroanthracenyl radicals (C 14 H 11...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2023-07, Vol.25 (29), p.19524-19531
Main Authors: Laws, Benjamin A, Krechkivska, Olha, Nauta, Klaas, Kable, Scott H, Schmidt, Timothy W
Format: Article
Language:English
Subjects:
Anharmonicity
Anthracene
Aromatic compounds
Broken symmetry
Charge transfer
Excitation spectra
Progressions
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Summary:Excitation spectra of protonated and deuteronated anthracene are obtained by triple-resonance dissociation spectroscopy. Very cold cations, protonated/deuteronated exclusively at the 9-position, are generated from two-colour two-photon threshold ionisation of 9-dihydroanthracenyl radicals (C 14 H 11 ). The excitation spectra reveal rich structure, not resolved in previous studies, that is assigned based on anharmonic and Herzberg-Teller coupling calculations. This work reveals that the excitation of protonated anthracene induces a symmetry-breaking intramolecular charge-transfer process along a Marcus-Hush coordinate, where the positively charged hole hops from the central bridging sp 2 carbon, onto one of the aromatic rings. Signatures of this charge-transfer event are observed in the excitation spectrum, through active Herzberg-Teller progressions. Triple-resonance dissociation spectra of protonated and deuteronated anthracene reveal signatures of an intramolecular charge-transfer event that occurs on the excited state surface.
ISSN:1463-9076
1463-9084
DOI:10.1039/d3cp02922k