Dynamics of π∗-resonances in anionic clusters of para-toluquinone

Bull, James N. ORCID: https://orcid.org/0000-0003-0953-1716 and Verlet, Jan R. R. (2017) Dynamics of π∗-resonances in anionic clusters of para-toluquinone. Physical Chemistry Chemical Physics, 19 (39). pp. 26589-26595. ISSN 1463-9076

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Frequency-resolved photoelectron spectroscopy applied to mass-selected cluster anions is an insightful approach to characterise the dynamics of π∗-resonances with microsolvation. Here, the technique is demonstrated with monomer, dimer and trimer radical anions of para-toluquinone (pTQ) over a ∼1 eV excitation window above the detachment threshold. The pTQ- spectra show similar resonances and dynamics to para-benzoquinone, a prototype electrophore. The dimer, (pTQ)2 -, has a π-stacked geometry and shows a competition between photodissociation and prompt autodetachment. The trimer, (pTQ)3 -, also has a π-stacked cluster geometry and shows vibrational autodetachment from a non-valence state up to ∼0.7 eV above-threshold, outcompeting dissociation. At higher photoexcitation energies, (pTQ)3 - shows monomer-like dynamics, blue-shifted in photoexcitation energy by the cluster cohesion energy. Overall, the study highlights the variety of non-adiabatic dynamics available to π∗-resonances and the profound changes that occur through clusterization with one and two monomers.

Item Type: Article
Uncontrolled Keywords: physics and astronomy(all),physical and theoretical chemistry ,/dk/atira/pure/subjectarea/asjc/3100
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Chemistry of Light and Energy
Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
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Depositing User: LivePure Connector
Date Deposited: 28 Feb 2019 16:30
Last Modified: 04 Mar 2024 17:46
URI: https://ueaeprints.uea.ac.uk/id/eprint/70061
DOI: 10.1039/c7cp03628k

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