Asymmetry in the Qy Fluorescence and Absorption Spectra of Chlorophyll <i>a</i> Pertaining to Exciton Dynamics.

Reimers, JR; Rätsep, M; Freiberg, A

Asymmetry in the Qy Fluorescence and Absorption Spectra of Chlorophyll <i>a</i> Pertaining to Exciton Dynamics.

Reimers, JR Rätsep, M Freiberg, A

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Publisher:: Frontiers Media
Publication Type:: Journal Article
Citation:: Frontiers in Chemistry, 2020, 8, pp. 588289-588289
Issue Date:: 2020-01

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Field	Value	Language
dc.contributor.author	Reimers, JR
dc.contributor.author	Rätsep, M
dc.contributor.author	Freiberg, A
dc.date.accessioned	2021-01-04T22:44:24Z
dc.date.available	2020-10-26
dc.date.available	2021-01-04T22:44:24Z
dc.date.issued	2020-01
dc.identifier.citation	Frontiers in Chemistry, 2020, 8, pp. 588289-588289
dc.identifier.issn	2296-2646
dc.identifier.issn	2296-2646
dc.identifier.uri	http://hdl.handle.net/10453/145070
dc.description.abstract	Significant asymmetry found between the high-resolution <i>Q</i> <sub>y</sub> emission and absorption spectra of chlorophyll-a is herein explained, providing basic information needed to understand photosynthetic exciton transport and photochemical reactions. The <i>Q</i> <sub>y</sub> spectral asymmetry in chlorophyll has previously been masked by interference in absorption from the nearby <i>Q</i> <sub>x</sub> transition, but this effect has recently been removed using extensive quantum spectral simulations or else by analytical inversion of absorption and magnetic circular dichroism data, allowing high-resolution absorption information to be accurately determined from fluorescence-excitation spectra. To compliment this, here, we measure and thoroughly analyze the high-resolution differential fluorescence line narrowing spectra of chlorophyll-a in trimethylamine and in 1-propanol. The results show that vibrational frequencies often change little between absorption and emission, yet large changes in line intensities are found, this effect also being strongly solvent dependent. Among other effects, the analysis in terms of four basic patterns of Duschinsky-rotation matrix elements, obtained using CAM-B3LYP calculations, predicts that a chlorophyll-a molecule excited into a specific vibrational level, may, without phase loss or energy relaxation, reemit the light over a spectral bandwidth exceeding 1,000 cm<sup>-1</sup> (0.13 eV) to influence exciton-transport dynamics.
dc.format	Electronic-eCollection
dc.language	eng
dc.publisher	Frontiers Media
dc.relation.ispartof	Frontiers in Chemistry
dc.relation.isbasedon	10.3389/fchem.2020.588289
dc.rights	info:eu-repo/semantics/openAccess
dc.title	Asymmetry in the Qy Fluorescence and Absorption Spectra of Chlorophyll <i>a</i> Pertaining to Exciton Dynamics.
dc.type	Journal Article
utslib.citation.volume	8
utslib.location.activity	Switzerland
pubs.organisational-group	/University of Technology Sydney/Faculty of Science
pubs.organisational-group	/University of Technology Sydney/Faculty of Science/School of Mathematical and Physical Sciences
pubs.organisational-group	/University of Technology Sydney
utslib.copyright.status	open_access	*
pubs.consider-herdc	false
dc.date.updated	2021-01-04T22:44:07Z
pubs.publication-status	Published
pubs.volume	8

Abstract:

Significant asymmetry found between the high-resolution Q _y emission and absorption spectra of chlorophyll-a is herein explained, providing basic information needed to understand photosynthetic exciton transport and photochemical reactions. The Q _y spectral asymmetry in chlorophyll has previously been masked by interference in absorption from the nearby Q _x transition, but this effect has recently been removed using extensive quantum spectral simulations or else by analytical inversion of absorption and magnetic circular dichroism data, allowing high-resolution absorption information to be accurately determined from fluorescence-excitation spectra. To compliment this, here, we measure and thoroughly analyze the high-resolution differential fluorescence line narrowing spectra of chlorophyll-a in trimethylamine and in 1-propanol. The results show that vibrational frequencies often change little between absorption and emission, yet large changes in line intensities are found, this effect also being strongly solvent dependent. Among other effects, the analysis in terms of four basic patterns of Duschinsky-rotation matrix elements, obtained using CAM-B3LYP calculations, predicts that a chlorophyll-a molecule excited into a specific vibrational level, may, without phase loss or energy relaxation, reemit the light over a spectral bandwidth exceeding 1,000 cm^-1 (0.13 eV) to influence exciton-transport dynamics.

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http://hdl.handle.net/10453/145070