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.
|Full text:||(AM) Accepted Manuscript|
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|Publisher Web site:||https://doi.org/10.1080/0144235X.2016.1203522|
|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: http://www.tandfonline.com/10.1080/0144235X.2016.1203522.|
|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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