James N. Bull
Dynamics of π*-resonances in anionic clusters of para-toluquinone
Bull, James N.; Verlet, Jan R.R.
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 | Sep 17, 2018 |
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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