J.N. Bull
Anion resonances and above-threshold dynamics of coenzyme Q0
Bull, J.N.; West, C.W.; Verlet, J.R.R.
Abstract
Temporary radical anions (resonances) of isolated co enzyme Q0 (CQ0) and their associated above-threshold dynamics have been studied using frequency-, angle-, and time-resolved photoelectron imaging (FAT-PI). Experimental energetics and dynamics are supported with ab initio calculations. All results support that CQ0 exhibits similar resonances and energetics compared with the smaller para-benzoquinone subunit, which is commonly considered as a prototype electrophore for larger biological para-quinone species. However, the above-threshold dynamics in CQ0 relative to para-benzoquinone show significantly enhanced prompt detachment compared with internal conversion, particularly around the photoexcitation energy of 3.10 eV. The change in dynamics can be attributed to a combination of an increase in the shape character of the optically-accessible resonance at this energy, a decrease in the autodetachment lifetime due to the higher density of states in the neutral, and a decrease in the probability that the wavepacket formed in the Franck–Condon window can access the local conical intersection in CQ0 over the timescale of autodetachment. Overall, this study serves as a clear example in understanding the trends in spectroscopy and dynamics in relating a simple prototypical para-quinone electrophore to a more complex biochemical species.
Citation
Bull, J., West, C., & Verlet, J. (2015). Anion resonances and above-threshold dynamics of coenzyme Q0. Physical Chemistry Chemical Physics, 17(24), 16125-16135. https://doi.org/10.1039/c5cp02145f
Journal Article Type | Article |
---|---|
Acceptance Date | May 19, 2015 |
Publication Date | Jun 28, 2015 |
Deposit Date | Jun 9, 2015 |
Publicly Available Date | May 19, 2016 |
Journal | Physical Chemistry Chemical Physics |
Print ISSN | 1463-9076 |
Electronic ISSN | 1463-9084 |
Publisher | Royal Society of Chemistry |
Peer Reviewed | Peer Reviewed |
Volume | 17 |
Issue | 24 |
Pages | 16125-16135 |
DOI | https://doi.org/10.1039/c5cp02145f |
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