Article | Published:

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

Nature Photonics volume 8, pages 650656 (2014) | Download Citation

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.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    & Optical detection and spectroscopy of single molecules in a solid. Phys. Rev. Lett. 62, 2535–2538 (1989).

  2. 2.

    & Single pentacene molecules detected by fluorescence excitation in a p-terphenyl crystal. Phys. Rev. Lett. 65, 2716–2719 (1990).

  3. 3.

    & Single molecules observed by near-field scanning optical microscopy. Science 262, 1422–1425 (1993).

  4. 4.

    , & Probing individual molecules with confocal fluorescence microscopy. Science 266, 1018–1021 (1994).

  5. 5.

    & Sorting single molecules: application to diagnostics and evolutionary biotechnology. Proc. Natl Acad. Sci. USA 91, 5740–5747 (1994).

  6. 6.

    & Single molecule optics. Ann. Rev. Phys. Chem. 55, 585–611 (2004).

  7. 7.

    , , & Single-molecule sensitivity in optical absorption at room temperature. J. Phys. Chem. Lett. 1, 3323–3327 (2010).

  8. 8.

    A dozen years of single-molecule spectroscopy in physics, chemistry, and biophysics. J. Phys. Chem. B 106, 910–927 (2002).

  9. 9.

    , , , & Nonlinear spectroscopy on a single quantum system: two-photon absorption of a single molecule. Science 271, 1703–1705 (1996).

  10. 10.

    , , & Room-temperature detection of a single molecule's absorption by photothermal contrast. Science 330, 353–356 (2010).

  11. 11.

    , & Theory of single-molecule spectroscopy: beyond the ensemble average. Ann. Rev. Phys. Chem. 55, 457–507 (2004).

  12. 12.

    Fluorescence spectroscopy of single biomolecules. Science 283, 1676–1683 (1999).

  13. 13.

    Single-molecule approach to enzymology. Single Molecules 2, 229–236 (2001).

  14. 14.

    , & Femtosecond coherence and quantum control of single molecules at room temperature. Nature Phys. 7, 172–177 (2011).

  15. 15.

    , , & Coherent control of single molecules at room temperature. Faraday Disc. 153, 51–60 (2011).

  16. 16.

    et al. Visualizing and controlling vibrational wave packets of single molecules. Nature 465, 905–908 (2010).

  17. 17.

    , , & Electronic coherences and vibrational wave-packets in single molecules studied with femtosecond phase-controlled spectroscopy. Phys. Chem. Chem. Phys. 13, 1888–1894 (2011).

  18. 18.

    & Antennas for light. Nature Photon. 5, 83–90 (2011).

  19. 19.

    & Surface Raman spectroelectrochemistry: part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode. J. Electroanal. Chem. 84, 1–20 (1977).

  20. 20.

    Theoretical-studies of surface enhanced Raman scattering. Acc. Chem. Res. 17, 370–376 (1984).

  21. 21.

    & Probing single molecules and single nanoparticles by surface-enhanced Raman scattering. Science 275, 1102–1106 (1997).

  22. 22.

    et al. Single molecule detection using surface-enhanced Raman scattering (SERS). Phys. Rev. Lett. 78, 1667–1670 (1997).

  23. 23.

    & A perspective on single molecule SERS: current status and future challenges. Phys. Chem. Chem. Phys. 10, 6079–6089 (2008).

  24. 24.

    et al. Chemical mapping of a single molecule by plasmon-enhanced Raman scattering. Nature 498, 82–86 (2013).

  25. 25.

    , , & Laser-induced shape changes of colloidal gold nanorods using femtosecond and nanosecond laser pulses. J. Phys. Chem. B 104, 6152–6163 (2000).

  26. 26.

    et al. Time-resolved surface-enhanced coherent sensing of nanoscale molecular complexes. Sci. Rep. 2, 891 (2012).

  27. 27.

    , , & Surface enhanced coherent anti-Stokes Raman scattering on nanostructured gold surfaces. Nano Lett. 11, 5339–5343 (2011).

  28. 28.

    et al. Surface-enhanced femtosecond CARS spectroscopy (SE-CARS) on pyridine. Vib. Spectrosc. 56, 9–12 (2011).

  29. 29.

    , , , & Tip-enhanced coherent anti-Stokes Raman scattering for vibrational nanoimaging. Phys. Rev. Lett. 92, 220801 (2004).

  30. 30.

    , , & Surface-enhanced femtosecond stimulated Raman spectroscopy. J. Phys. Chem. Lett. 2, 1199–1203 (2011).

  31. 31.

    Principles of Nonlinear Optical Spectroscopy (Oxford Univ. Press, 1995).

  32. 32.

    , & Time resolved coherent anti-Stokes Raman scattering of I2 isolated in matrix argon: vibrational dynamics on the ground electronic state. J. Chem. Phys. 114, 4131–4140 (2001).

  33. 33.

    The Quantum Theory of Light (Oxford Univ. Press, 2000).

  34. 34.

    et al. Structure enhancement factor relationships in single gold nanoantennas by surface-enhanced Raman excitation spectroscopy. J. Am. Chem. Soc. 135, 301–308 (2013).

  35. 35.

    et al. Structure–activity relationships in gold nanoparticle dimers and trimers for surface-enhanced Raman spectroscopy. J. Am. Chem. Soc. 132, 10903–10910 (2010).

  36. 36.

    et al. High sensitivity surface-enhanced Raman scattering in solution using engineered silver nanosphere dimers. J. Phys. Chem. C 115, 15900–15907 (2011).

  37. 37.

    , , & A frequency domain existence proof of single-molecule surface-enhanced Raman spectroscopy. J. Am. Chem. Soc. 129, 16249–16256 (2007).

  38. 38.

    , , , & Directional Raman scattering from single molecules in the feed gaps of optical antennas. Nano Lett. 13, 2194–2198 (2013).

  39. 39.

    et al. Surface-enhanced Raman trajectories on a nano-dumbbell: transition from field to charge transfer plasmons as the spheres fuse. ACS Nano 6, 10343–10354 (2012).

  40. 40.

    , , & A surface-enhanced hyper-Raman and surface-enhanced Raman scattering study of trans-1,2-bis(4-pyridyl)ethylene adsorbed onto silver film over nanosphere electrodes. Vibrational assignments: experiment and theory. J. Chem. Phys. 104, 4313–4323 (1996).

  41. 41.

    , , & Intramolecular insight into adsorbate-substrate interactions via low-temperature, ultrahigh-vacuum tip-enhanced Raman spectroscopy. J. Am. Chem. Soc. 136, 3881–3887 (2014).

  42. 42.

    & Optical frequency mixing at coupled gold nanoparticles. Phys. Rev. Lett. 98, 026104 (2007).

  43. 43.

    , , , & Four-wave mixing microscopy of nanostructures. Adv. Opt. Photon. 3, 1–52 (2011).

  44. 44.

    , , , & Coherent Fano resonances in a plasmonic nanocluster enhance optical four-wave mixing. Proc. Natl Acad. Sci. USA 110, 9215–9219 (2013).

  45. 45.

    Speckle Phenomena in Optics: Theory and Applications. (Roberts & Co., 2007).

  46. 46.

    Proof without prejudice: use of the Kolmogorov–Smirnov test for the analysis of histograms from flow systems and other sources. J. Histochem. Cytochem. 25, 935–941 (1977).

  47. 47.

    , & Quantum tomography of a molecular bond in ice. J. Chem. Phys. 139, 034201 (2013).

  48. 48.

    , , & The manipulation of massive ro-vibronic superpositions using time-frequency-resolved coherent anti-Stokes Raman scattering (TFRCARS): from quantum control to quantum computing. Chem. Phys. 266, 323–351 (2001).

  49. 49.

    , , & An implementation of the Deutsch–Jozsa algorithm on molecular vibronic coherences through four-wave mixing: a theoretical study. Chem. Phys. Lett. 360, 459–465 (2002).

  50. 50.

    , & Quantum logic gates in iodine vapor using time–frequency resolved coherent anti-Stokes Raman scattering: a theoretical study. Mol. Phys. 104, 1249–1266 (2006).

Download references

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.

Author information

Affiliations

  1. Department of Chemistry, University of California, Irvine, California 92697, 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, University of Jyväskylä, Finland

    • Eero Hulkko

Authors

  1. Search for Steven Yampolsky in:

  2. Search for Dmitry A. Fishman in:

  3. Search for Shirshendu Dey in:

  4. Search for Eero Hulkko in:

  5. Search for Mayukh Banik in:

  6. Search for Eric O. Potma in:

  7. Search for Vartkess A. Apkarian in:

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.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Eric O. Potma.

Supplementary information

PDF files

  1. 1.

    Supplementary information

    Supplementary information

Videos

  1. 1.

    Supplementary movie

    Supplementary movie

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nphoton.2014.143

Further reading