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Ultrafast dynamics of temporary anions probed through the prism of photodetachment.

Anstöter, C. S. and Bull, J. N. and Verlet, J. R. R. (2016) 'Ultrafast dynamics of temporary anions probed through the prism of photodetachment.', International reviews in physical chemistry., 35 (4). pp. 509-538.


The recently developed method of frequency-, angle-, and time-resolved photoelectron imaging (FAT-PI) applied to the study of the dynamics of resonances of open-shell anions is reviewed. The basic principles of the method and its experimental realisation are outlined. The dynamics of a number of radical quinone anions is then considered. Firstly, we show for para-benzoquinone how frequency- and angle-resolved photoelectron imaging provides finger-prints of the dynamics of resonances and then how time-resolved photoelectron imaging yields deep mechanistic insight into the relaxation dynamics of the resonances. The effect of chemical substitutions of the para-quinone electrophore on the dynamics of resonances is discussed. Increasing the conjugation leads to a greatly enhanced ability for resonances to decay to the ground electronic state of the radical anion. Using time-resolved photoelectron spectroscopy, it is shown that the dynamics are facilitated by a bound valence state of the anion. The addition of electron donating methoxy groups leads to a reduced ability to access the ground state compared to para-benzoquinone. Both time-resolved dynamics and calculations provide a rationale for these observations. We consider the benefits and limitations of FAT-PI and its complementarity to 2D electron spectroscopy.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Publisher statement:This is an Accepted Manuscript of an article published by Taylor & Francis Group in International Reviews in Physical Chemistry on 08/08/2016, available online at:
Date accepted:08 June 2016
Date deposited:31 October 2016
Date of first online publication:08 August 2016
Date first made open access:08 August 2018

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