Visualizing and controlling vibrational wave packets of single molecules

Abstract

The active steering of the pathways taken by chemical reactions and the optimization of energy conversion processes1,2,3 provide striking examples of the coherent control of quantum interference through the use of shaped laser pulses. Experimentally, coherence is usually established by synchronizing a subset of molecules in an ensemble4,5,6,7 with ultra-short laser pulses8. But in complex systems where even chemically identical molecules exist with different conformations and in diverse environments, the synchronized subset will have an intrinsic inhomogeneity that limits the degree of coherent control that can be achieved. A natural—and, indeed, the ultimate—solution to overcoming intrinsic inhomogeneities is the investigation of the behaviour of one molecule at a time. The single-molecule approach9,10 has provided useful insights into phenomena as diverse as biomolecular interactions11,12,13, cellular processes14 and the dynamics of supercooled liquids15 and conjugated polymers16. Coherent state preparation of single molecules has so far been restricted to cryogenic conditions17, whereas at room temperature only incoherent vibrational relaxation pathways have been probed18. Here we report the observation and manipulation of vibrational wave-packet interference in individual molecules at ambient conditions. We show that adapting the time and phase distribution of the optical excitation field to the dynamics of each molecule results in a high degree of control, and expect that the approach can be extended to achieve single-molecule coherent control in other complex inhomogeneous systems.

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Figure 1: Ultrafast coherent excitation of single molecules.
Figure 2: Single-molecule wave-packet interference.
Figure 3: Phase control of single-molecule wave packets.
Figure 4: Single-molecule time-phase coherent excitation maps.

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Acknowledgements

We thank P. Fendel from Menlo Systems for lending us an Octavius system and for technical assistance. We are grateful to Biophotonic Solutions Inc. for collaborating with us in developing the double-pass pulse shaper. We appreciate discussions with A. G. Curto and M. Castro López. This work was supported by the ‘Molecular walker’ project of the Koerber foundation (Hamburg) and by the Spanish Ministry of Science and Innovation (CSD2007-046-NanoLight.es and MAT2006-08184).

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D.B., F.D.S. and N.F.v.H. conceived and designed the experiments. D.B., F.K. and R.H. constructed the experimental set-up. D.B. and F.D.S. carried out the measurements and analysis. D.B., F.D.S. and T.H.T. performed control experiments. Y.A. and K.M. provided the fluorescent molecules. F.D.S., D.B. and N.F.v.H. wrote the manuscript.

Corresponding authors

Correspondence to Fernando D. Stefani or Niek F. van Hulst.

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The authors declare no competing financial interests.

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Brinks, D., Stefani, F., Kulzer, F. et al. Visualizing and controlling vibrational wave packets of single molecules. Nature 465, 905–908 (2010). https://doi.org/10.1038/nature09110

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