Assignment of the Q-Bands of the Chlorophylls: Coherence Loss via Q x-Q y Mixing

Reimers, JR; Cai, ZL; Kobayashi, R; Rätsep, M; Freiberg, A; Krausz, E

Assignment of the Q-Bands of the Chlorophylls: Coherence Loss via Q x-Q y Mixing

Reimers, JR

Cai, ZL Kobayashi, R Rätsep, M Freiberg, A Krausz, E

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Publication Type:: Journal Article
Citation:: Scientific Reports, 2013, 3
Issue Date:: 2013-10-14

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Field	Value	Language
dc.contributor.author	Reimers, JR https://orcid.org/0000-0001-5157-7422	en_US
dc.contributor.author	Cai, ZL	en_US
dc.contributor.author	Kobayashi, R	en_US
dc.contributor.author	Rätsep, M	en_US
dc.contributor.author	Freiberg, A	en_US
dc.contributor.author	Krausz, E	en_US
dc.date.available	2013-09-03	en_US
dc.date.issued	2013-10-14	en_US
dc.identifier.citation	Scientific Reports, 2013, 3	en_US
dc.identifier.uri	http://hdl.handle.net/10453/28194
dc.identifier.uri	http://hdl.handle.net/10453/33057
dc.description.abstract	We provide a new and definitive spectral assignment for the absorption, emission, high-resolution fluorescence excitation, linear dichroism, and/or magnetic circular dichroism spectra of 32 chlorophyllides in various environments. This encompases all data used to justify previous assignments and provides a simple interpretation of unexplained complex decoherence phenomena associated with Q x → Q y relaxation. Whilst most chlorophylls conform to the Gouterman model and display two independent transitions Q x (S 2) and Q y (S 1), strong vibronic coupling inseparably mixes these states in chlorophyll-a. This spreads x-polarized absorption intensity over the entire Q-band system to influence all exciton-transport, relaxation and coherence properties of chlorophyll-based photosystems. The fraction of the total absorption intensity attributed to Q x ranges between 7% and 33%, depending on chlorophyllide and coordination, and is between 10% and 25% for chlorophyll-a. CAM-B3LYP density-functional-theory calculations of the band origins, relative intensities, vibrational Huang-Rhys factors, and vibronic coupling strengths fully support this new assignment.	en_US
dc.relation.ispartof	Scientific Reports	en_US
dc.relation.isbasedon	10.1038/srep02761	en_US
dc.subject.mesh	Chlorophyll	en_US
dc.subject.mesh	Spectrometry, Fluorescence	en_US
dc.subject.mesh	Circular Dichroism	en_US
dc.subject.mesh	Absorption	en_US
dc.subject.mesh	Quantum Theory	en_US
dc.subject.mesh	Optical Phenomena	en_US
dc.subject.mesh	Magnetic Phenomena	en_US
dc.subject.mesh	Ether	en_US
dc.title	Assignment of the Q-Bands of the Chlorophylls: Coherence Loss via Q x-Q y Mixing	en_US
dc.type	Journal Article
utslib.citation.volume	3	en_US
utslib.for	0601 Biochemistry and Cell Biology	en_US
pubs.embargo.period	Not known	en_US
pubs.organisational-group	/University of Technology Sydney
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
utslib.copyright.status	open_access
pubs.publication-status	Published	en_US
pubs.volume	3	en_US

Abstract:

We provide a new and definitive spectral assignment for the absorption, emission, high-resolution fluorescence excitation, linear dichroism, and/or magnetic circular dichroism spectra of 32 chlorophyllides in various environments. This encompases all data used to justify previous assignments and provides a simple interpretation of unexplained complex decoherence phenomena associated with Q x → Q y relaxation. Whilst most chlorophylls conform to the Gouterman model and display two independent transitions Q x (S 2) and Q y (S 1), strong vibronic coupling inseparably mixes these states in chlorophyll-a. This spreads x-polarized absorption intensity over the entire Q-band system to influence all exciton-transport, relaxation and coherence properties of chlorophyll-based photosystems. The fraction of the total absorption intensity attributed to Q x ranges between 7% and 33%, depending on chlorophyllide and coordination, and is between 10% and 25% for chlorophyll-a. CAM-B3LYP density-functional-theory calculations of the band origins, relative intensities, vibrational Huang-Rhys factors, and vibronic coupling strengths fully support this new assignment.

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http://hdl.handle.net/10453/28194