Abstract
Quantum-mechanical phenomena, such as electronic coherence and entanglement, play a key role in several remarkably efficient natural processes including ultrafast electronic energy transfer and charge separation in photosynthetic light-harvesting. To gain insight into such dynamic processes of biomolecules it is vital to reveal relations between structural and quantum-mechanical properties. However, ensemble experiments targeting ultrafast coherences are hampered by the large intrinsic heterogeneity in these systems at physiological conditions, and single-molecule techniques have not been available until now. Here we show, by employing femtosecond pulse-shaping techniques, that quantum coherences in single organic molecules can be created, probed and manipulated at ambient conditions even in highly disordered solid environments. We find broadly distributed coherence decay times for different individual molecules giving direct insight into the structural heterogeneity of the local surroundings. Most importantly, we induce Rabi oscillations and control the coherent superposition state in a single molecule, thus carrying out a basic femtosecond single-qubit operation at room temperature.
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References
Ladd, T. D. et al. Quantum computers. Nature 464, 45–53 (2010).
Buluta, I. & Nori, F. Quantum simulators. Science 326, 108–111 (2009).
Bennett, C. H. & DiVincenzo, D. P. Quantum information and computation. Nature 404, 247–255 (2000).
Hosaka, K. et al. Ultrafast Fourier transform with a femtosecond-laser-driven molecule. Phys. Rev. Lett. 104, 180501 (2010).
Lee, H., Cheng, Y. C. & Fleming, G. R. Coherence dynamics in photosynthesis: Protein protection of excitonic coherence. Science 316, 1462–1465 (2007).
Engel, G. S. et al. Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems. Nature 446, 782–786 (2007).
Collini, E. et al. Coherently wired light-harvesting in photosynthetic marine algae at ambient temperature. Nature 463, 644–647 (2010).
Panitchayangkoon, G. et al. Long-lived quantum coherence in photosynthetic complexes at physiological temperature. Proc. Natl Acad. Sci. USA 107, 12766–12770 (2010).
Scholes, G. D. Quantum-coherent electronic energy transfer: Did Nature think of it first? J. Phys. Chem. Lett. 1, 2–8 (2010).
Sarovar, M., Ishizaki, A., Fleming, G. R. & Whaley, K. B. Quantum entanglement in photosynthetic light-harvesting complexes. Nature Phys. 6, 462–467 (2010).
Abramavicius, D. & Mukamel, S. Quantum oscillatory exciton migration in photosynthetic reaction centres. J. Chem. Phys. 133, 064510 (2010).
Mukamel, S. Signatures of quasiparticle entanglement in multidimensional nonlinear optical spectroscopy of aggregates. J. Chem. Phys. 132, 241105 (2010).
van Dijk, E. M. H. P. et al. Single-molecule pump-probe detection resolves ultrafast pathways in individual and coupled quantum systems. Phys. Rev. Lett. 94, 078302 (2005).
Brinks, D. et al. Visualizing and controlling vibrational wave packets of single molecules. Nature 465, 905–908 (2010).
Gerhard, I. et al. Coherent state preparation and observation of Rabi oscillations in a single molecule. Phys. Rev. A 79, 011402 (2009).
Wrigge, G. et al. Efficient coupling of photon to a single molecule and the observation of its resonance fluorescence. Nature Phys. 4, 60–66 (2008).
Kamada, H. et al. Exciton Rabi oscillation in a single quantum dot. Phys. Rev. Lett. 87, 246401 (2001).
Htoon, H. et al. Interplay of Rabi oscillations and quantum interference in semiconductor quantum dots. Phys. Rev. Lett. 88, 087401 (2002).
Childress, L. et al. Coherent dynamics of coupled electron and nuclear spin qubits in diamond. Science 314, 281–285 (2006).
Min, W. et al. Imaging chromophores with undetectable fluorescence by stimulated emission microscopy. Nature 461, 1105–1109 (2009).
Chong, S., Min, W. & Xie, X. S. Ground-state depletion microscopy: Detection sensitivity of single-molecule optical absorption at room temperature. J. Phys. Chem. Lett. 1, 3316–3322 (2010).
Kukura, P., Celebrano, M., Renn, A. & Sandoghdar, V. Single-molecule sensitivity in optical absorption at room temperature. J. Phys. Chem. Lett. 1, 3323–3327 (2010).
Gaiduk, A., Yorulmaz, M., Ruijgrok, P. V. & Orrit, M. Room-temperature detection of a single molecule’s absorption by photothermal contrast. Science 330, 353–356 (2010).
Feynman, R. P., Vernon, F. L. & Hellwarth, R. W. Geometrical representation of the Schrodinger equation for solving maser problems. J. Appl. Phys. 28, 49–52 (1957).
Allen, L. & Eberly, J. H. Optical Resonance and Two-Level Atoms (Dover, 1987).
Loudon, R. The Quantum Theory of Light (Oxford Univ. Press, 2000).
Zewail, A. H. Optical molecular dephasing: Principles of and probings by coherent laser spectroscopy. Acc. Chem. Res. 13, 360–368 (1980).
Schweitzer, G. et al. Intramolecular directional energy transfer processes in dendrimers containing perylene and terrylene chromophores. J. Phys. Chem. A 107, 3199–3207 (2007).
Fourkas, J. T. et al. Picosecond time-scale phase-related optical pulses: Measurement of sodium optical coherence decay by observation of incoherent fluorescence. J. Opt. Soc. Am. B 6, 1905–1910 (1989).
Brewer, R. G. & Genack, A. Z. Optical coherent transients by laser frequency switching. Phys. Rev. Lett. 36, 959–962 (1976).
Balasubramanian, G. et al. Ultralong spin coherence time in isotopically engineered diamond. Nature Mater. 8, 383–387 (2009).
Mais, S. et al. Terrylenediimide: A novel fluorophore for single-molecule spectroscopy and microscopy from 1.4 K to room temperature. J. Phys. Chem. A 101, 8435–8440 (1997).
Macklin, J. J., Trautman, J. K., Harris, T. D. & Brus, L. E. Imaging and time-resolved spectroscopy of single molecules at an interface. Science 272, 255–258 (1996).
Acknowledgements
We thank T. H. Taminiau, F. D. Stefani and F. Kulzer for discussions and assistance with the experimental set-up, and K. Müllen for providing the molecules. Financial support by the Körber Foundation (Hamburg), the Spanish Ministry of Science and Innovation (CSD2007-046-NanoLight.es and MAT2006-08184) and the European Union (FP6, Bio-Light-Touch) is gratefully acknowledged.
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R.H. carried out the measurements, analysed the data and conducted the simulations. D.B. and R.H. constructed the experimental set-up and carried out control experiments. R.H., D.B. and N.F.v.H. conceived and designed the experiment, and discussed the data. R.H. wrote the paper. N.F.v.H. supervised the project.
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Hildner, R., Brinks, D. & van Hulst, N. Femtosecond coherence and quantum control of single molecules at room temperature. Nature Phys 7, 172–177 (2011). https://doi.org/10.1038/nphys1858
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DOI: https://doi.org/10.1038/nphys1858
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