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Resonances of the anthracenyl anion probed by frequency-resolved photoelectron imaging of collision-induced dissociated anthracene carboxylic acid.

Stanley, Laurence H. and Anstöter, Cate S. and Verlet, Jan R. R. (2017) 'Resonances of the anthracenyl anion probed by frequency-resolved photoelectron imaging of collision-induced dissociated anthracene carboxylic acid.', Chemical science., 8 (4). 3054-3061 .

Abstract

Resonances in polyaromatic hydrocarbon (PAH) anions are key intermediates in a number of processes such as electron transfer in organic electronics and electron attachment in the interstellar medium. Here we present a frequency- and angle-resolved photoelectron imaging study of the 9-anthracenyl anion generated through collision induced dissociation (CID) of its electrosprayed deprotonated anthracene carboxylic acid anion. We show that a number of π* resonances are active in the first 2.5 eV above the threshold. The photoelectron spectra and angular distributions revealed that nuclear dynamics compete with autodetachment for one of the resonances, while higher-lying resonances were dominated by prompt autodetachment. Based on electronic structure calculations, these observations were accounted for on the basis of the expected autodetachment rates of the resonances. Virtually no ground state recovery was observed, suggesting that the smallest deprotonated PAH that leads to ground state recovery is the tetracenyl anion, for which clear thermionic emission has been observed. The use of CID and photodissociation of organic carboxylic acid anions is discussed as a route to studying the dynamics of resonances in larger PAH anions.

Item Type:Article
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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1039/C6SC05405F
Publisher statement:This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
Date accepted:01 February 2017
Date deposited:11 July 2017
Date of first online publication:02 February 2017
Date first made open access:No date available

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