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

Bull, James N.; Verlet, Jan R.R.

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Authors

James N. Bull



Abstract

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.

Citation

Bull, J. N., & Verlet, J. R. (2017). Dynamics of π*-resonances in anionic clusters of para-toluquinone. Physical Chemistry Chemical Physics, 19(39), 26589-26595. https://doi.org/10.1039/c7cp03628k

Journal Article Type Article
Acceptance Date Sep 17, 2017
Online Publication Date Sep 18, 2017
Publication Date Oct 21, 2017
Deposit Date Dec 12, 2017
Publicly Available Date Mar 29, 2024
Journal Physical Chemistry Chemical Physics
Print ISSN 1463-9076
Electronic ISSN 1463-9084
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 19
Issue 39
Pages 26589-26595
DOI https://doi.org/10.1039/c7cp03628k

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