Non-radiative relaxation of photoexcited chlorophylls: theoretical and experimental study

Scientific Reports
William P BrickerYang Zhao

Abstract

Nonradiative relaxation of high-energy excited states to the lowest excited state in chlorophylls marks the first step in the process of photosynthesis. We perform ultrafast transient absorption spectroscopy measurements, that reveal this internal conversion dynamics to be slightly slower in chlorophyll B than in chlorophyll A. Modeling this process with non-adiabatic excited state molecular dynamics simulations uncovers a critical role played by the different side groups in the two molecules in governing the intramolecular redistribution of excited state wavefunction, leading, in turn, to different time-scales. Even given smaller electron-vibrational couplings compared to common organic conjugated chromophores, these molecules are able to efficiently dissipate about 1 eV of electronic energy into heat on the timescale of around 200 fs. This is achieved via selective participation of specific atomic groups and complex global migration of the wavefunction from the outer to inner ring, which may have important implications for biological light-harvesting function.

References

Nov 11, 1999·Proceedings of the National Academy of Sciences of the United States of America·S TretiakS Mukamel
Oct 18, 2001·Journal of the American Chemical Society·J M PecourtB Kohler
Mar 25, 2004·Journal of the American Chemical Society·Henk FidderErik T J Nibbering
Jul 9, 2004·Biochimica Et Biophysica Acta·Ivo H M van StokkumRienk van Grondelle
Feb 17, 2006·Physical Chemistry Chemical Physics : PCCP·Juha Linnanto, Jouko Korppi-Tommola
Nov 13, 2008·Annual Review of Physical Chemistry·Yuan-Chung Cheng, Graham R Fleming
Jan 12, 2011·The Journal of Physical Chemistry. B·Tammie NelsonSergei Tretiak
May 17, 2011·Biochimica Et Biophysica Acta·Alexander V RubanChristopher D P Duffy
Sep 24, 2011·Nature Chemistry·Gregory D ScholesRienk van Grondelle
Feb 11, 2012·The Journal of Chemical Physics·Tammie NelsonSergei Tretiak
Jul 5, 2012·The Journal of Chemical Physics·Jun YeJianshu Cao
Sep 11, 2012·The Journal of Chemical Physics·Shi-Jie XiongYang Zhao
Sep 19, 2012·The Journal of Physical Chemistry. a·Miguel A SolerSebastian Fernandez-Alberti
Mar 14, 2013·The Journal of Physical Chemistry. B·Junkuo GaoYang Zhao
Jul 26, 2013·The Journal of Chemical Physics·Daisuke KosumiHideki Hashimoto
Sep 27, 2013·Scientific Reports·Jeffrey R ReimersElmars Krausz
Dec 20, 2013·Journal of the Royal Society, Interface·Francesca FassioliGregory D Scholes
Mar 29, 2014·Accounts of Chemical Research·Tammie NelsonSergei Tretiak
Jun 18, 2014·Nature Chemical Biology·Roberta Croce, Herbert van Amerongen
Sep 3, 2014·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Jan P GötzeWalter Thiel
May 11, 2010·Journal of Chemical Theory and Computation·Mario R Silva-Junior, Walter Thiel

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Citations

Aug 27, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Lipeng ChenYang Zhao
Feb 20, 2016·The Journal of Physical Chemistry Letters·Nicholas H C Lewis, Graham R Fleming
Dec 15, 2015·The Journal of Physical Chemistry. B·Prathamesh Mahesh ShenaiYang Zhao
Aug 11, 2016·Scientific Reports·R Franklin-MergarejoS Fernandez-Alberti
May 10, 2017·The Journal of Physical Chemistry. B·Fulu ZhengYang Zhao
Jun 13, 2017·The Journal of Physical Chemistry Letters·Tammie NelsonSergei Tretiak
Jun 20, 2018·Physical Chemistry Chemical Physics : PCCP·Victor M FreixasDmitrii Shalashilin
Oct 10, 2018·Physical Chemistry Chemical Physics : PCCP·Evgenii TitovRoland Mitrić
Sep 14, 2017·Scientific Reports·Elena MeneghinElisabetta Collini
Apr 25, 2020·International Journal of Molecular Sciences·Elisa Fresch, Elisabetta Collini
Jun 2, 2017·Scientific Reports·Sotiris PapadatosVangelis Daskalakis
Nov 28, 2020·Nature Communications·Eric A ArsenaultGraham R Fleming
Nov 12, 2018·Biochimica Et Biophysica Acta. Bioenergetics·David BínaTomáš Polívka
Jul 20, 2018·Journal of Photochemistry and Photobiology. B, Biology·J SemerM Navrátil
Jul 22, 2017·The Journal of Physical Chemistry. a·Alan Celestino, Alexander Eisfeld
Jan 19, 2019·The Journal of Physical Chemistry. B·M Faisal KhyasudeenHowe-Siang Tan
Jul 25, 2018·The Journal of Physical Chemistry. a·Daniel A HartzlerSergei Savikhin
Nov 6, 2018·The Journal of Physical Chemistry. a·Andrew E SifainSergei Tretiak
May 2, 2020·The Journal of Physical Chemistry Letters·Levi LystromSvetlana Kilina
Jul 9, 2020·Journal of Chemical Theory and Computation·Walter MaloneSergei Tretiak
Sep 4, 2021·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Dmitry A CherepanovAlexey Yu Semenov
Oct 21, 2021·The Journal of Physical Chemistry Letters·Johan F GalindoSebastian Fernandez-Alberti

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Software Mentioned

ChlA
Glotaran
ESMD
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