Mechanistic Regimes of Vibronic Transport in a Heterodimer and the Design Principle of Incoherent Vibronic Transport in Phycobiliproteins

Doran I.G. Bennett, Pavel Malý, Christoph Kreisbeck, Rienk Van Grondelle, Alán Aspuru-Guzik

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

Following the observation of coherent oscillations in nonlinear spectra of photosynthetic pigment protein complexes, in particular, phycobilliproteins such as PC645, coherent vibronic transport has been suggested as a design principle for novel light-harvesting materials. Vibronic transport between energetically remote pigments is coherent when the presence of a vibration resonant with the electronic energy gap supports transient delocalization between the electronic excited states. We establish the mechanism of vibronic transport for a model heterodimer across a wide range of molecular parameter values. The resulting mechanistic map demonstrates that the molecular parameters of phycobiliproteins in fact support incoherent vibronic transport. This result points to an important design principle: Incoherent vibronic transport is more efficient than a coherent mechanism when energetic disorder exceeds the coupling between the donor and vibrationally excited acceptor states. Finally, our results suggest that the role of coherent vibronic transport in pigment protein complexes should be reevaluated.

Original languageEnglish
Pages (from-to)2665-2670
Number of pages6
JournalJournal of Physical Chemistry Letters
Volume9
Issue number10
Early online date23 Apr 2018
DOIs
Publication statusPublished - 17 May 2018

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Phycobiliproteins
pigments
Pigments
Excited states
proteins
Proteins
resonant vibration
electronics
Energy gap
disorders
oscillations
excitation

Cite this

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title = "Mechanistic Regimes of Vibronic Transport in a Heterodimer and the Design Principle of Incoherent Vibronic Transport in Phycobiliproteins",
abstract = "Following the observation of coherent oscillations in nonlinear spectra of photosynthetic pigment protein complexes, in particular, phycobilliproteins such as PC645, coherent vibronic transport has been suggested as a design principle for novel light-harvesting materials. Vibronic transport between energetically remote pigments is coherent when the presence of a vibration resonant with the electronic energy gap supports transient delocalization between the electronic excited states. We establish the mechanism of vibronic transport for a model heterodimer across a wide range of molecular parameter values. The resulting mechanistic map demonstrates that the molecular parameters of phycobiliproteins in fact support incoherent vibronic transport. This result points to an important design principle: Incoherent vibronic transport is more efficient than a coherent mechanism when energetic disorder exceeds the coupling between the donor and vibrationally excited acceptor states. Finally, our results suggest that the role of coherent vibronic transport in pigment protein complexes should be reevaluated.",
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Mechanistic Regimes of Vibronic Transport in a Heterodimer and the Design Principle of Incoherent Vibronic Transport in Phycobiliproteins. / Bennett, Doran I.G.; Malý, Pavel; Kreisbeck, Christoph; Van Grondelle, Rienk; Aspuru-Guzik, Alán.

In: Journal of Physical Chemistry Letters, Vol. 9, No. 10, 17.05.2018, p. 2665-2670.

Research output: Contribution to JournalArticleAcademicpeer-review

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