Impact of cavity on molecular ionization spectra

Ionization phenomena have been widely studied for decades. With the advent of cavity technology, the question arises how quantum light affects molecular ionization. As the ionization spectrum is recorded from the neutral ground state, it is usually possible to choose cavities which exert negligible...

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Hauptverfasser: Fábri, Csaba (VerfasserIn) , Halász, Gábor J. (VerfasserIn) , Cederbaum, Lorenz S. (VerfasserIn) , Vibók, Ágnes (VerfasserIn)
Dokumenttyp: Article (Journal) Editorial
Sprache:Englisch
Veröffentlicht: April 22, 2024
In: The journal of physical chemistry letters
Year: 2024, Jahrgang: 15, Heft: 17, Pages: 4655-4661
ISSN:1948-7185
DOI:10.1021/acs.jpclett.4c00247
Online-Zugang:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.jpclett.4c00247
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Verfasserangaben:Csaba Fábri, Gábor J. Halász, Lorenz S. Cederbaum, and Ágnes Vibók
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Zusammenfassung:Ionization phenomena have been widely studied for decades. With the advent of cavity technology, the question arises how quantum light affects molecular ionization. As the ionization spectrum is recorded from the neutral ground state, it is usually possible to choose cavities which exert negligible effect on the neutral ground state, but have significant impact on the ion and the ionization spectrum. Particularly interesting are cases where the ion exhibits conical intersections between close-lying electronic states, which gives rise to substantial nonadiabatic effects. Assuming single-molecule strong coupling, we demonstrate that vibrational modes irrelevant in the absence of a cavity play a decisive role when the molecule is in the cavity. Here, dynamical symmetry breaking is responsible for the ion-cavity coupling and high symmetry enables control of the coupling via molecular orientation relative to the cavity field polarization. Significant impact on the spectrum by the cavity is found and shown to even substantially increase for less symmetric molecules.
Beschreibung:Gesehen am 28.10.2024
Beschreibung:Online Resource
ISSN:1948-7185
DOI:10.1021/acs.jpclett.4c00247