Anharmonic Molecular Motion Drives Resonance Energy Transfer in peri-Arylene Dyads
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F20%3A10421368" target="_blank" >RIV/00216208:11320/20:10421368 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=Qz1YgEjPuE" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=Qz1YgEjPuE</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.3389/fchem.2020.579166" target="_blank" >10.3389/fchem.2020.579166</a>
Alternative languages
Result language
angličtina
Original language name
Anharmonic Molecular Motion Drives Resonance Energy Transfer in peri-Arylene Dyads
Original language description
Spectral and dynamical properties of molecular donor-acceptor systems strongly depend on the steric arrangement of the constituents with exciton coupling J as a key control parameter. In the present work we study two peri-arylene based dyads with orthogonal and parallel transition dipoles for donor and acceptor moieties, respectively. We show that the anharmonic multi-well character of the orthogonal dyad's intramolecular potential explains findings from both stationary and time-resolved absorption experiments. While for a parallel dyad, standard quantum chemical estimates of J at 0 K are in good agreement with experimental observations, J becomes vanishingly small for the orthogonal dyad, in contrast to its ultrafast experimental transfer times. This discrepancy is not resolved even by accounting for harmonic fluctuations along normal coordinates. We resolve this problem by supplementing quantum chemical approaches with dynamical sampling of fluctuating geometries. In contrast to the moderate Gaussian fluctuations of J for the parallel dyad, fluctuations for the orthogonal dyad are found to follow non-Gaussian statistics leading to significantly higher effective J in good agreement with experimental observations. In effort to apply a unified framework for treating the dynamics of optical coherence and excitonic populations of both dyads, we employ a vibronic approach treating electronic and selected vibrational degrees on an equal footing. This vibronic model is used to model absorption and fluorescence spectra as well as donor-acceptor transport dynamics and covers the more traditional categories of Förster and Redfield transport as limiting cases.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10300 - Physical sciences
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Frontiers in Chemistry [online]
ISSN
2296-2646
e-ISSN
—
Volume of the periodical
8
Issue of the periodical within the volume
23.11.2020
Country of publishing house
CH - SWITZERLAND
Number of pages
12
Pages from-to
579166
UT code for WoS article
000595942800001
EID of the result in the Scopus database
2-s2.0-85097277618