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Seeing a single molecule vibrate through time-resolved coherent anti-Stokes Raman scattering

Nature Photonics volume 8, pages 650–656 (2014)Cite this article

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Abstract

The motion of chemical bonds within molecules can be observed in real time in the form of vibrational wave packets prepared and interrogated through ultrafast nonlinear spectroscopy. Such nonlinear optical measurements are commonly performed on large ensembles of molecules and, as such, are limited to the extent that ensemble coherence can be maintained. Here, we describe vibrational wave packet motion on single molecules, recorded through time-resolved, surface-enhanced, coherent anti-Stokes Raman scattering. The sensitivity required to detect the motion of a single molecule under ambient conditions is achieved by equipping the molecule with a dipolar nano-antenna (a gold dumbbell). In contrast with measurements in ensembles, the vibrational coherence on a single molecule does not undergo pure dephasing. It develops phase fluctuations with characteristic statistics. We present the time evolution of discretely sampled statistical states, and highlight the unique information content in the characteristic, early-time probability distribution function of the signal.

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Figure 1: SERS of BPE molecules on dumbbell antennas.
Figure 2: tr-CARS microscopy of individual molecule-dumbbells structures.
Figure 3: Stable CARS under minimum photodamaging conditions.
Figure 4: tr-CARS traces in the single-molecule limit.
Figure 5: PDFs calculated for different realizations of the number of molecules N, number of modes V and variance of the spectral fluctuations σ.

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Acknowledgements

The authors thank R. P. Van Duyne for providing the samples, P. Z. El-Khoury for DFT calculations for BPE and N. Apkarian for pointing out the KS analysis. SEM and TEM work was performed at the Laboratory for Electron and X-ray Instrumentation (LEXI) at UC Irvine. This work was made possible by the National Science Foundation Center for Chemical Innovation on Chemistry at the Space–Time Limit (grant CHE-0802913). E.H. is supported by the Academy of Finland Decision no. 265502.

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Authors and Affiliations

  1. Department of Chemistry, University of California, Irvine, 92697, California, USA

    Steven Yampolsky, Dmitry A. Fishman, Shirshendu Dey, Eero Hulkko, Mayukh Banik, Eric O. Potma & Vartkess A. Apkarian

  2. Department of Chemistry, PO Box 35, FI-40014

    Eero Hulkko

  3. University of Jyväskylä, Finland

    Eero Hulkko

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Contributions

S.Y. and D.A.F. conducted the tr-CARS measurements. M.B., E.H. and S.D. carried out the Raman and SEM/TEM measurements. S.Y. and V.A.A. performed the analysis. E.O.P. and V.A.A. conceived the idea for the work and wrote the manuscript.

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Correspondence to Eric O. Potma.

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Yampolsky, S., Fishman, D., Dey, S. et al. Seeing a single molecule vibrate through time-resolved coherent anti-Stokes Raman scattering. Nature Photon 8, 650–656 (2014). https://doi.org/10.1038/nphoton.2014.143

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