Quantum Coherence Controls the Charge Separation in a Prototypical Artificial Light-harvesting System

Overview

Journal Nat Commun

Specialty Biology

Date 2013 Mar 21

PMID 23511467

Citations 32

Authors

Carlo Andrea Rozzi

Sarah Maria Falke

Nicola Spallanzani

Angel Rubio

Elisa Molinari

Daniele Brida

Margherita Maiuri

Giulio Cerullo

Heiko Schramm

Jens Christoffers

Christoph Lienau

Affiliations

Soon will be listed here.

Abstract

The efficient conversion of light into electricity or chemical fuels is a fundamental challenge. In artificial photosynthetic and photovoltaic devices, this conversion is generally thought to happen on ultrafast, femto-to-picosecond timescales and to involve an incoherent electron transfer process. In some biological systems, however, there is growing evidence that the coherent motion of electronic wavepackets is an essential primary step, raising questions about the role of quantum coherence in artificial devices. Here we investigate the primary charge-transfer process in a supramolecular triad, a prototypical artificial reaction centre. Combining high time-resolution femtosecond spectroscopy and time-dependent density functional theory, we provide compelling evidence that the driving mechanism of the photoinduced current generation cycle is a correlated wavelike motion of electrons and nuclei on a timescale of few tens of femtoseconds. We highlight the fundamental role of the interface between chromophore and charge acceptor in triggering the coherent wavelike electron-hole splitting.

Citing Articles

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References

Scholes G, Fleming G, Olaya-Castro A, van Grondelle R . Lessons from nature about solar light harvesting. Nat Chem. 2011; 3(10):763-74. DOI: 10.1038/nchem.1145. View

Castro A, Marques M, Rubio A . Propagators for the time-dependent Kohn-Sham equations. J Chem Phys. 2004; 121(8):3425-33. DOI: 10.1063/1.1774980. View

Lee H, Cheng Y, Fleming G . Coherence dynamics in photosynthesis: protein protection of excitonic coherence. Science. 2007; 316(5830):1462-5. DOI: 10.1126/science.1142188. View

Spallanzani N, Rozzi C, Varsano D, Baruah T, Pederson M, Manghi F . Photoexcitation of a light-harvesting supramolecular triad: a time-dependent DFT study. J Phys Chem B. 2009; 113(16):5345-9. DOI: 10.1021/jp900820q. View

Alonso J, Andrade X, Echenique P, Falceto F, Prada-Gracia D, Rubio A . Efficient formalism for large-scale ab initio molecular dynamics based on time-dependent density functional theory. Phys Rev Lett. 2008; 101(9):096403. DOI: 10.1103/PhysRevLett.101.096403. View

Genovese L, Deutsch T, Neelov A, Goedecker S, Beylkin G . Efficient solution of Poisson's equation with free boundary conditions. J Chem Phys. 2006; 125(7):074105. DOI: 10.1063/1.2335442. View

Gratzel M . Photoelectrochemical cells. Nature. 2001; 414(6861):338-44. DOI: 10.1038/35104607. View

Baruah T, Pederson M . DFT Calculations on Charge-Transfer States of a Carotenoid-Porphyrin-C60 Molecular Triad. J Chem Theory Comput. 2015; 5(4):834-43. DOI: 10.1021/ct900024f. View

Duncan W, Prezhdo O . Theoretical studies of photoinduced electron transfer in dye-sensitized TiO2. Annu Rev Phys Chem. 2006; 58:143-84. DOI: 10.1146/annurev.physchem.58.052306.144054. View

10.

Collini E, Wong C, Wilk K, Curmi P, Brumer P, Scholes G . Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature. Nature. 2010; 463(7281):644-7. DOI: 10.1038/nature08811. View

11.

Bahr , Kuciauskas , Liddell , Moore , Gust . Driving force and electronic coupling effects on photoinduced electron transfer in a fullerene-based molecular triad. Photochem Photobiol. 2000; 72(5):598-611. DOI: 10.1562/0031-8655(2000)072<0598:dfaece>2.0.co;2. View

12.

Abramavicius D, Mukamel S . Energy-transfer and charge-separation pathways in the reaction center of photosystem II revealed by coherent two-dimensional optical spectroscopy. J Chem Phys. 2010; 133(18):184501. PMC: 4109822. DOI: 10.1063/1.3493580. View

13.

Andrade X, Castro A, Zueco D, Alonso J, Echenique P, Falceto F . Modified Ehrenfest Formalism for Efficient Large-Scale ab initio Molecular Dynamics. J Chem Theory Comput. 2015; 5(4):728-42. DOI: 10.1021/ct800518j. View

14.

Cerullo G, Polli D, Lanzani G, De Silvestri S, Hashimoto H, Cogdell R . Photosynthetic light harvesting by carotenoids: detection of an intermediate excited state. Science. 2002; 298(5602):2395-8. DOI: 10.1126/science.1074685. View

15.

Carcel C, Laha J, Loewe R, Thamyongkit P, Schweikart K, Misra V . Porphyrin architectures tailored for studies of molecular information storage. J Org Chem. 2004; 69(20):6739-50. DOI: 10.1021/jo0498260. View

16.

Polli D, Altoe P, Weingart O, Spillane K, Manzoni C, Brida D . Conical intersection dynamics of the primary photoisomerization event in vision. Nature. 2010; 467(7314):440-3. DOI: 10.1038/nature09346. View

17.

Varsano D, Marini A, Rubio A . Optical saturation driven by exciton confinement in molecular chains: a time-dependent density-functional theory approach. Phys Rev Lett. 2008; 101(13):133002. DOI: 10.1103/PhysRevLett.101.133002. View

18.

Blankenship R, Tiede D, Barber J, Brudvig G, Fleming G, Ghirardi M . Comparing photosynthetic and photovoltaic efficiencies and recognizing the potential for improvement. Science. 2011; 332(6031):805-9. DOI: 10.1126/science.1200165. View

19.

Polli D, Luer L, Cerullo G . High-time-resolution pump-probe system with broadband detection for the study of time-domain vibrational dynamics. Rev Sci Instrum. 2007; 78(10):103108. DOI: 10.1063/1.2800778. View

20.

Ishizaki A, Fleming G . Theoretical examination of quantum coherence in a photosynthetic system at physiological temperature. Proc Natl Acad Sci U S A. 2009; 106(41):17255-60. PMC: 2762676. DOI: 10.1073/pnas.0908989106. View