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Issue 24, 2015
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Anion resonances and above-threshold dynamics of coenzyme Q0

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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.

Graphical abstract: Anion resonances and above-threshold dynamics of coenzyme Q0

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Publication details

The article was received on 13 Apr 2015, accepted on 19 May 2015 and first published on 27 May 2015


Article type: Paper
DOI: 10.1039/C5CP02145F
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Citation: Phys. Chem. Chem. Phys., 2015,17, 16125-16135
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    Anion resonances and above-threshold dynamics of coenzyme Q0

    J. N. Bull, C. W. West and J. R. R. Verlet, Phys. Chem. Chem. Phys., 2015, 17, 16125
    DOI: 10.1039/C5CP02145F

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