Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Visualizing vibrational normal modes of a single molecule with atomically confined light

Nature volume 568, pages 78–82 (2019)Cite this article

Subjects

Abstract

The internal vibrations of molecules drive the structural transformations that underpin chemistry and cellular function. While vibrational frequencies are measured by spectroscopy, the normal modes of motion are inferred through theory because their visualization would require microscopy with ångström-scale spatial resolution—nearly three orders of magnitude smaller than the diffraction limit in optics1. Using a metallic tip to focus light and taking advantage of the surface-enhanced Raman effect2 to amplify the signal from individual molecules, tip-enhanced Raman spectromicroscopy (TER-SM)3,4 reaches the requisite sub-molecular spatial resolution5, confirming that light can be confined in picocavities6,7,8,9,10 and anticipating the direct visualization of molecular vibrations11,12,13. Here, by using TER-SM at the precisely controllable junction of a cryogenic ultrahigh-vacuum scanning tunnelling microscope14,15,16, we show that ångström-scale resolution is attained at subatomic separation between the tip atom and a molecule in the quantum tunnelling regime of plasmons6,8,9,17. We record vibrational spectra within a single molecule, obtain images of normal modes and atomically parse the intramolecular charges and currents driven by vibrations. Our analysis provides a paradigm for optics in the atomistic near-field.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Confinement of TERS signal.
Fig. 2: Spectral variation and principal component analysis.
Fig. 3: Visualization of vibrational normal modes.
Fig. 4: Close-ups of TER-SM images and their simulations.

Similar content being viewed by others

Data availability

The data supporting the findings of this study are available within the paper. Experimental source data for Figs. 1–4 are provided with the paper.

References

  1. Betzig, E. Nobel lecture: single molecules, cells, and super-resolution optics. Rev. Mod. Phys. 87, 1153–1168 (2015).

    Article  ADS  CAS  Google Scholar 

  2. Jeanmaire, D. L. & Van Duyne, R. P. Surface Raman spectroelectrochemistry: part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode. J. Electroanal. Chem. 84, 1–20 (1977).

    Article  CAS  Google Scholar 

  3. Jiang, N. et al. Tip-enhanced Raman spectroscopy: from concepts to practical applications. Chem. Phys. Lett. 659, 16–24 (2016).

    Article  ADS  CAS  Google Scholar 

  4. Stöckle, R. M., Suh, Y. D., Deckert, V. & Zenobi, R. Nanoscale chemical analysis by tip-enhanced Raman spectroscopy. Chem. Phys. Lett. 318, 131–136 (2000).

    Article  ADS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  6. Zhang, P., Feist, J., Rubio, A., García-González, P. & García-Vidal, F. J. Ab initio nanoplasmonics: the impact of atomic structure. Phys. Rev. B 90, 161407 (2014).

    Article  ADS  Google Scholar 

  7. Trautmann, S. et al. A classical description of subnanometer resolution by atomic features in metallic structures. Nanoscale 9, 391–401 (2017).

    Article  CAS  Google Scholar 

  8. Urbieta, M. et al. Atomic-scale lightning rod effect in plasmonic picocavities: a classical view to a quantum effect. ACS Nano 12, 585–595 (2018).

    Article  CAS  Google Scholar 

  9. Chen, X. & Jensen, L. Morphology dependent near-field response in atomistic plasmonic nanocavities. Nanoscale 10, 11410–11417 (2018).

    Article  CAS  Google Scholar 

  10. Benz, F. et al. Single-molecule optomechanics in ‘picocavities’. Science 354, 726–729 (2016).

    Article  ADS  CAS  Google Scholar 

  11. Duan, S. et al. Theoretical modeling of plasmon-enhanced Raman images of a single molecule with subnanometer resolution. J. Am. Chem. Soc. 137, 9515–9518 (2015).

    Article  CAS  Google Scholar 

  12. Duan, S., Tian, G. & Luo, Y. Visualization of vibrational modes in real space by tip-enhanced non-resonant Raman spectroscopy. Angew. Chem. Int. Ed. 55, 1041–1045 (2016).

    Article  CAS  Google Scholar 

  13. Liu, P., Chulhai, D. V. & Jensen, L. Single-molecule imaging using atomistic near-field tip-enhanced Raman spectroscopy. ACS Nano 11, 5094–5102 (2017).

    Article  CAS  Google Scholar 

  14. Pozzi, E. A. et al. Ultrahigh-vacuum tip-enhanced Raman spectroscopy. Chem. Rev. 117, 4961–4982 (2017).

    Article  CAS  Google Scholar 

  15. Steidtner, J. & Pettinger, B. Tip-enhanced Raman spectroscopy and microscopy on single dye molecules with 15 nm resolution. Phys. Rev. Lett. 100, 236101 (2008).

    Article  ADS  Google Scholar 

  16. Chiang, N. et al. Molecular-resolution interrogation of a porphyrin monolayer by ultrahigh vacuum tip-enhanced Raman and fluorescence spectroscopy. Nano Lett. 15, 4114–4120 (2015).

    Article  ADS  CAS  Google Scholar 

  17. Savage, K. J. et al. Revealing the quantum regime in tunnelling plasmonics. Nature 491, 574–577 (2012).

    Article  ADS  CAS  Google Scholar 

  18. Moskovits, M. Criterion for determining resolving power in the optical near field. J. Nanophotonics 11, 046018 (2017).

    Article  ADS  Google Scholar 

  19. Lee, J. et al. Tip-enhanced Raman spectromicroscopy of Co(ii)-tetraphenylporphyrin on Au(111): toward the chemists’ microscope. ACS Nano 11, 11466–11474 (2017).

    Article  CAS  Google Scholar 

  20. Tallarida, N., Rios, L., Apkarian, V. A. & Lee, J. Isomerization of one molecule observed through tip-enhanced Raman spectroscopy. Nano Lett. 15, 6386–6394 (2015).

    Article  ADS  CAS  Google Scholar 

  21. Tallarida, N., Lee, J. & Apkarian, V. A. Tip-enhanced Raman spectromicroscopy on the angstrom scale: bare and CO-terminated Ag tips. ACS Nano 11, 11393–11401 (2017).

    Article  CAS  Google Scholar 

  22. Hugall, J. T. & Baumberg, J. J. Demonstrating photoluminescence from au is electronic inelastic light scattering of a plasmonic metal: the origin of SERS backgrounds. Nano Lett. 15, 2600–2604 (2015).

    Article  ADS  CAS  Google Scholar 

  23. Dey, S. et al. Observation and analysis of Fano-like lineshapes in the Raman spectra of molecules adsorbed at metal interfaces. Phys. Rev. B 93, 035411 (2016).

    Article  ADS  Google Scholar 

  24. Lee, J., Tallarida, N., Chen, X., Jensen, L. & Apkarian, V. A. Microscopy with a single-molecule scanning electrometer. Sci. Adv. 4, eaat5472 (2018).

    Article  ADS  Google Scholar 

  25. Le Ru, E. C. & Etchegoin, P. G. Rigorous justification of the |E|4 enhancement factor in surface enhanced Raman spectroscopy. Chem. Phys. Lett. 423, 63–66 (2006).

    Article  ADS  Google Scholar 

  26. Lee, J. et al. Orbiting orbitals: visualization of vibronic motion at a conical intersection. J. Phys. Chem. A 117, 11655–11664 (2013).

    Article  CAS  Google Scholar 

  27. Banik, M. 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).

    Article  CAS  Google Scholar 

  28. Di Santo, G. et al. Conformational adaptation and electronic structure of 2H-tetraphenylporphyrin on Ag(111) during Fe metalation. J. Phys. Chem. C 115, 4155–4162 (2011).

    Article  Google Scholar 

  29. Smoluchowski, R. Anisotropy of the electronic work function of metals. Phys. Rev. 60, 661–674 (1941).

    Article  ADS  CAS  Google Scholar 

  30. Hirshfeld, F. L. Bonded-atom fragments for describing molecular charge densities. Theor. Chim. Acta 44, 129–138 (1977).

    Article  CAS  Google Scholar 

  31. Marenich, A. V., Cramer, C. J. & Truhlar, D. G. Reduced and quenched polarizabilities of interior atoms in molecules. Chem. Sci. 4, 2349–2356 (2013).

    Article  CAS  Google Scholar 

  32. Gough, K. M., Srivastava, H. K. & Belohorcová, K. Analysis of Raman trace scattering intensities in alkanes with the theory of atoms in molecules. J. Chem. Phys. 98, 9669–9677 (1993).

    Article  ADS  CAS  Google Scholar 

  33. Frisch, M. J. et al. Gaussian 09, Revision C.01 (Gaussian, Inc., Wallingford, 2010).

    Google Scholar 

Download references

Acknowledgements

This research was supported by the NSF Center for Chemical Innovation dedicated to Chemistry at the Space-Time Limit (CHE-1414466). Theoretical calculations were performed on the UCI Greenplanet cluster system (CHE-0840513). We thank P. El-Khoury for advice on DFT calculations. We have benefited from discussions with L. Jensen, X. Chen and P. Liu.

Reviewer information

Nature thanks Eric Le Ru and the other anonymous reviewer(s) for their contribution to the peer review of this work.

Author information

Author notes

  1. Kevin T. Crampton

    Present address: Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, USA

  2. Nicholas Tallarida

    Present address: Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA

Authors and Affiliations

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

    Joonhee Lee, Kevin T. Crampton, Nicholas Tallarida & V. Ara Apkarian

Authors
  1. Joonhee Lee
    View author publications

    Search author on:PubMed Google Scholar

  2. Kevin T. Crampton
    View author publications

    Search author on:PubMed Google Scholar

  3. Nicholas Tallarida
    View author publications

    Search author on:PubMed Google Scholar

  4. V. Ara Apkarian
    View author publications

    Search author on:PubMed Google Scholar

Contributions

J.L. and K.T.C. carried out experimental work and data analysis. J.L. performed theoretical simulations. N.T. produced nanoscopically smooth silver tips and performed preliminary principal component analysis. J.L. and V.A.A. conceived and coordinated the project and authored the paper with input from all co-authors.

Corresponding authors

Correspondence to Joonhee Lee or V. Ara Apkarian.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data figures and tables

Extended Data Fig. 1 Conformational transformation of CoTPP on Cu(100).

a, An imaging sequence starting at −0.5 V is followed by repeated scans at –12 mV. The size of the images is 35 × 35 Å2. The pressing scanning condition at −12 mV leads to planarity of the phenyl groups. b, Optimized geometry of a free CoTPP molecule and flat geometry of an adsorbed CoTPP molecule with artificially flattened phenyl rings. c, Lattice registry of the flat CoTPP and the marker CO molecule, which adsorbs on the copper on-top site.

Extended Data Fig. 2 Disappearance of the Kondo resonance.

The Kondo resonance observed on the saddled CoTPP adsorbed on the Au(111) surface disappears on the flat CoTPP adsorbed on the Cu(100) surface. The gap distances are set at 1 nA, +0.2 V and 1 nA, −0.2 V for Au and Cu, respectively.

Extended Data Fig. 3 Gap dependence of Raman intensity and vibrational frequency.

a, b, Measurements on cobalt (a) and pyrrole (b). Colour-coded vertical grid lines in the leftmost graph indicate vibrational modes analysed in terms of intensity and frequency shift in the middle and right panels, respectively. The extracted powers n from the curve fit (I = az−n) are indicated in the corresponding colours.

Extended Data Fig. 4 Maps of omitted normal modes.

The modes presented here are extensively delocalized and do not yield unique assignments.

Extended Data Fig. 5 Dominance of Δαzz in the observed TERS.

Raman images of the 388-cm−1 mode, simulated using out-of-plane (zz) and in-plane (xx) polarizability differences, and the map of the xx component of the polarizability at equilibrium (α0,xx). The Δαzz component reproduces the experiment, whereas the Δαxx fails despite its large magnitude. The charge accumulation at the edges upon polarization is demonstrated in both Δαxx and α0,xx. This trend applies to all of the observed normal modes.

Extended Data Fig. 6 Vibrational Stark effect of the C–H stretch.

Evolution of the C–H stretch upon tuning of the integration window. The image size and resolution are 28 × 28 Å2 and 80 × 80 pixels, respectively. Images are low-pass-filtered for clarity.

Extended Data Fig. 7 Schematic diagram for the resolution of near-field optical microscopy.

a, Local electric field along the z axis, Ez, arising from a charge. Only the z component is considered because in-plane dipoles induced by tangential components are cancelled by their images in the metallic substrate. b, Comparison between the fourth power of the Coulomb field distribution (q = 1) and equivalent Gaussian with the associated FWHM value.

Extended Data Fig. 8 Selection rules of atomistic TERS.

Top right, orientationally averaged Raman spectrum of the free molecule. The intensities of the selected vibrational modes shown in Fig. 3 are indicated by red dots and dashed lines. Bottom right, atomic polarizability differences and their colour-coded amplitudes in atomic units. The colour represents the phase of the out-of-plane atomic dynamic dipole associated with \({\alpha }_{zz}^{i}\). Left, while a nonlocal excitation leads to the cancellation of induced dipoles (top), the atomistic near field samples each radiating vertical dipole that is reinforced by its image (bottom). h0 and σ0 are Rayleigh length and waist, respectively, as defined in ‘Gaussian optics’ in Methods.

Source data

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lee, J., Crampton, K.T., Tallarida, N. et al. Visualizing vibrational normal modes of a single molecule with atomically confined light. Nature 568, 78–82 (2019). https://doi.org/10.1038/s41586-019-1059-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41586-019-1059-9

This article is cited by

Comments

Commenting on this article is now closed.

  1. Henry Rzepa

    I am intruiged by the nature of the "flattened" species on e.g. the Cu surface. The article seems to imply a CoTPP with D4h symmetry {This suggests that the vibronic functions are complex-valued in this state, as expected for Jahn-Teller active degenerate orbitals of the planar porphyrin}. For such a geometry, there would be eight pairs of close H...H contacts, separated by about 0.8Å if no geometric relaxation occurs, or ~1.34Å if it does. Since the shortest known H...H non bonded contact is 1.5Å, such a geometry seems unlikely.

    I have computed the geometries and energies of a range of charges and spin states for CoTPP (see DOI: 10.14469/hpc/5559 for discussion, DOI: 10.14469/hpc/5486 for FAIR data and 10.14469/hpc/5561 for a FAIR data table), finding that simply rotating the phenyl groups does not result in a planar species. If D4h symmetry is enforced, this species is calculated to be around 176 kcal/mol higher in free energy than the relaxed free molecule. The most likely candidate resulting from phenyl group rotation is a species with C2v symmetry as a triplet state anion.

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing