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      Effect of Time-Delayed Feedback on the Interaction of a Dimer System with its Environment

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      1 , , 1 , 2 , 1 , 3
      Scientific Reports
      Nature Publishing Group UK

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          Abstract

          In this work, we report modeling of non-Markovian open quantum systems, consisting of an excitonic dimer that displays memory effect due to time delayed interaction with its environment. We, indeed investigate the effect of these time delays on quantum coherence and excitation dynamical behavior in the time domain generally considered for photosynthetic experiments (few hundred femtoseconds). In particular, we show that the coherence is maintained for periods proportional to time delays. Additionally, if delay is taken into account, coupling to the environment can be tuned to lower values, unlike in previous studies. This kind of intriguing effect can, therefore, when generalized to complete systems, permit more control on the experimental parameters, which may lead to more accurate description of the photosynthetic energy transfer functioning and subsequent applications in artificial photovoltaic research.

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          Two-dimensional femtosecond spectroscopy.

          The simplest two-dimensional (2D) spectra show how excitation with one (variable) frequency affects the spectrum at all other frequencies, thus revealing the molecular connections between transitions. Femtosecond 2D Fourier transform (2D FT) spectra are more flexible and share some of the remarkable properties of their conceptual parent, 2D FT nuclear magnetic resonance. When 2D FT spectra are experimentally separated into real absorptive and imaginary refractive parts, the time resolution and frequency resolution can both reach the uncertainty limit set for each resonance by the sample itself. Coherent four-level contributions to the signal provide new molecular phase information, such as relative signs of transition dipoles. The nonlinear response can be picked apart by selecting a single coherence pathway (e.g., specifying the relative signs of energy level difference frequencies during different time intervals as in the photon echo). Because molecules are frozen on the femtosecond timescale, femtosecond 2D FT experiments can separate a distribution of instantaneous molecular environments and intramolecular geometries as inhomogeneous broadening. This review provides an introduction to two-dimensional Fourier transform experiments exploiting second- and third-order vibrational and electronic nonlinearities.
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            Theoretical examination of quantum coherence in a photosynthetic system at physiological temperature.

            The observation of long-lived electronic coherence in a photosynthetic pigment-protein complex, the Fenna-Matthews-Olson (FMO) complex, is suggestive that quantum coherence might play a significant role in achieving the remarkable efficiency of photosynthetic electronic energy transfer (EET), although the data were acquired at cryogenic temperature [Engel GS, et al. (2007) Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems. Nature 446:782-786]. In this paper, the spatial and temporal dynamics of EET through the FMO complex at physiological temperature are investigated theoretically. The numerical results reveal that quantum wave-like motion persists for several hundred femtoseconds even at physiological temperature, and suggest that the FMO complex may work as a rectifier for unidirectional energy flow from the peripheral light-harvesting antenna to the reaction center complex by taking advantage of quantum coherence and the energy landscape of pigments tuned by the protein scaffold. A potential role of quantum coherence is to overcome local energetic traps and aid efficient trapping of electronic energy by the pigments facing the reaction center complex.
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              Coherent intrachain energy migration in a conjugated polymer at room temperature.

              The intermediate coupling regime for electronic energy transfer is of particular interest because excitation moves in space, as in a classical hopping mechanism, but quantum phase information is conserved. We conducted an ultrafast polarization experiment specifically designed to observe quantum coherent dynamics in this regime. Conjugated polymer samples with different chain conformations were examined as model multichromophoric systems. The data, recorded at room temperature, reveal coherent intrachain (but not interchain) electronic energy transfer. Our results suggest that quantum transport effects occur at room temperature when chemical donor-acceptor bonds help to correlate dephasing perturbations.
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                Author and article information

                Contributors
                mfarhat@hbku.edu.qa
                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group UK (London )
                2045-2322
                13 November 2017
                13 November 2017
                2017
                : 7
                : 15468
                Affiliations
                [1 ]ISNI 0000 0001 0516 2170, GRID grid.418818.c, Qatar Environment and Energy Research Institute (QEERI), Hamad Bin Khalifa University, Qatar Foundation, ; Doha, Qatar
                [2 ]ISNI 0000 0004 1937 2197, GRID grid.169077.e, Department of Chemistry, Department of Physics and Birck Nanotechnology Center, Purdue University, ; West Lafayette, IN 47907 USA
                [3 ]ISNI 0000 0004 1789 3191, GRID grid.452146.0, College of Science and Engineering, Hamad Bin Khalifa University, ; Doha, Qatar
                Article
                15185
                10.1038/s41598-017-15185-z
                5684406
                29133789
                da703472-1d61-4582-bef7-64028273c961
                © The Author(s) 2017

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 21 June 2017
                : 20 October 2017
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