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

Bull, James N. 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.

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.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1039/C7CP03628K
Date accepted:17 September 2017
Date deposited:13 December 2017
Date of first online publication:18 September 2017
Date first made open access:17 September 2018

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