C.S. Anstöter
Ultrafast dynamics of temporary anions probed through the prism of photodetachment
Anstöter, C.S.; Bull, J.N.; Verlet, J.R.R.
Abstract
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.
Citation
Anstöter, C., Bull, J., & Verlet, J. (2016). Ultrafast dynamics of temporary anions probed through the prism of photodetachment. International Reviews in Physical Chemistry, 35(4), 509-538. https://doi.org/10.1080/0144235x.2016.1203522
Journal Article Type | Article |
---|---|
Acceptance Date | Jun 8, 2016 |
Online Publication Date | Aug 8, 2016 |
Publication Date | Oct 1, 2016 |
Deposit Date | Oct 31, 2016 |
Publicly Available Date | Mar 29, 2024 |
Journal | International Reviews in Physical Chemistry |
Print ISSN | 0144-235X |
Electronic ISSN | 1366-591X |
Publisher | Taylor and Francis Group |
Peer Reviewed | Peer Reviewed |
Volume | 35 |
Issue | 4 |
Pages | 509-538 |
DOI | https://doi.org/10.1080/0144235x.2016.1203522 |
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Copyright 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.
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