Wiebeler_2017_Ultrafast_JPCL_AAM.pdf (1.9 MB)
Ultrafast electronic energy transfer in an orthogonal molecular dyad
journal contribution
posted on 2018-03-16, 13:52 authored by Christian Wiebeler, Felix PlasserFelix Plasser, Gordon J. Hedley, Arvydas Ruseckas, Ifor D. W. Samuel, Stefan Schumacher© 2017 American Chemical Society. Understanding electronic energy transfer (EET) is an important ingredient in the development of artificial photosynthetic systems and photovoltaic technologies. Although EET is at the heart of these applications and crucially influences their light-harvesting efficiency, the nature of EET over short distances for covalently bound donor and acceptor units is often not well understood. Here we investigate EET in an orthogonal molecular dyad (BODT4), in which simple models fail to explain the very origin of EET. On the basis of nonadiabatic ab initio molecular dynamics calculations and ultrafast fluorescence experiments, we gain detailed microscopic insights into the ultrafast electrovibrational dynamics following photoexcitation. Our analysis offers molecular-level insights into these processes and reveals that it takes place on time scales ≲100 fs and occurs through an intermediate charge-transfer state.
Funding
C.W. and S.S. thank the German Research Foundation (DFG: GRK 1464) for financial support and PC2 for computing time. S.S. acknowledges support through the Heisenberg programme of the DFG. F.P. acknowledges support by the VSC Research Center funded by the Austrian Federal Ministry of Science, Research, and Economy (bmwfw). The St Andrews group acknowledges support from the European Research Council (grant number 321305) and the Engineering and Physical Sciences Research Council (grant EP/L017008/1). I.D.W.S. also acknowledges support from a Royal Society Wolfson Research Merit Award.
History
School
- Science
Department
- Chemistry
Published in
Journal of Physical Chemistry LettersVolume
8Issue
5Pages
1086 - 1092Citation
WIEBELER, C. ...et al., 2017. Ultrafast electronic energy transfer in an orthogonal molecular dyad. Journal of Physical Chemistry Letters, 8(5), pp. 1086-1092.Publisher
© American Chemical Society (ACS)Version
- AM (Accepted Manuscript)
Publisher statement
This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/Acceptance date
2017-02-16Publication date
2017Notes
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpclett.7b00089eISSN
1948-7185Publisher version
Language
- en