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

doi:10.1038/s41586-019-1059-9

. 2019 Apr;568(7750):78-82.

doi: 10.1038/s41586-019-1059-9. Epub 2019 Apr 3.

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

Joonhee Lee¹, Kevin T Crampton^{2

3}, Nicholas Tallarida^{2

4}, V Ara Apkarian⁵

Affiliations

¹ Department of Chemistry, University of California, Irvine, CA, USA. joonhee@uci.edu.
² Department of Chemistry, University of California, Irvine, CA, USA.
³ Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, USA.
⁴ Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA.
⁵ Department of Chemistry, University of California, Irvine, CA, USA. aapkaria@uci.edu.

PMID: 30944493
DOI: 10.1038/s41586-019-1059-9

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

Joonhee Lee et al. Nature. 2019 Apr.

. 2019 Apr;568(7750):78-82.

doi: 10.1038/s41586-019-1059-9. Epub 2019 Apr 3.

Authors

Joonhee Lee¹, Kevin T Crampton^{2

3}, Nicholas Tallarida^{2

4}, V Ara Apkarian⁵

Affiliations

¹ Department of Chemistry, University of California, Irvine, CA, USA. joonhee@uci.edu.
² Department of Chemistry, University of California, Irvine, CA, USA.
³ Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, USA.
⁴ Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA, USA.
⁵ Department of Chemistry, University of California, Irvine, CA, USA. aapkaria@uci.edu.

PMID: 30944493
DOI: 10.1038/s41586-019-1059-9

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 picocavities^6-10 and anticipating the direct visualization of molecular vibrations^11-13. Here, by using TER-SM at the precisely controllable junction of a cryogenic ultrahigh-vacuum scanning tunnelling microscope^14-16, we show that ångström-scale resolution is attained at subatomic separation between the tip atom and a molecule in the quantum tunnelling regime of plasmons^6,8,9,17. 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.

PubMed Disclaimer

Comment in

Snapshots of vibrating molecules.
Le Ru EC. Le Ru EC. Nature. 2019 Apr;568(7750):36-37. doi: 10.1038/d41586-019-00987-0. Nature. 2019. PMID: 30944489 No abstract available.

Cited by

Fluorescence from a single-molecule probe directly attached to a plasmonic STM tip.
Friedrich N, Rosławska A, Arrieta X, Kaiser K, Romeo M, Le Moal E, Scheurer F, Aizpurua J, Borisov AG, Neuman T, Schull G. Friedrich N, et al. Nat Commun. 2024 Nov 10;15(1):9733. doi: 10.1038/s41467-024-53707-2. Nat Commun. 2024. PMID: 39523359 Free PMC article.
Impact of Surface Enhanced Raman Spectroscopy in Catalysis.
Stefancu A, Aizpurua J, Alessandri I, Bald I, Baumberg JJ, Besteiro LV, Christopher P, Correa-Duarte M, de Nijs B, Demetriadou A, Frontiera RR, Fukushima T, Halas NJ, Jain PK, Kim ZH, Kurouski D, Lange H, Li JF, Liz-Marzán LM, Lucas IT, Meixner AJ, Murakoshi K, Nordlander P, Peveler WJ, Quesada-Cabrera R, Ringe E, Schatz GC, Schlücker S, Schultz ZD, Tan EX, Tian ZQ, Wang L, Weckhuysen BM, Xie W, Ling XY, Zhang J, Zhao Z, Zhou RY, Cortés E. Stefancu A, et al. ACS Nano. 2024 Oct 29;18(43):29337-29379. doi: 10.1021/acsnano.4c06192. Epub 2024 Oct 14. ACS Nano. 2024. PMID: 39401392 Free PMC article. Review.
Nanoscale Imaging of Palladium-Enhanced Photocatalytic Reduction of 4-Nitrothiophenol on Tungsten Disulfide Nanoplates.
Patil SJ, Kurouski D. Patil SJ, et al. Nano Lett. 2024 Oct 7;24(41):13004-9. doi: 10.1021/acs.nanolett.4c03702. Online ahead of print. Nano Lett. 2024. PMID: 39373895 Free PMC article.
Selective excitation of vibrations in a single molecule.
Luo Y, Sheng S, Pisarra M, Martin-Jimenez A, Martin F, Kern K, Garg M. Luo Y, et al. Nat Commun. 2024 Aug 14;15(1):6983. doi: 10.1038/s41467-024-51419-1. Nat Commun. 2024. PMID: 39143046 Free PMC article.
Nanoscale Chemical Probing of Metal-Supported Ultrathin Ferrous Oxide via Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy.
Liu D, Li L, Jiang N. Liu D, et al. Chem Biomed Imaging. 2024 Mar 21;2(5):345-351. doi: 10.1021/cbmi.4c00015. eCollection 2024 May 27. Chem Biomed Imaging. 2024. PMID: 38817320 Free PMC article.

See all "Cited by" articles

References

1. Betzig, E. Nobel lecture: single molecules, cells, and super-resolution optics. Rev. Mod. Phys. 87, 1153–1168 (2015). - DOI
1. 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). - DOI
1. Jiang, N. et al. Tip-enhanced Raman spectroscopy: from concepts to practical applications. Chem. Phys. Lett. 659, 16–24 (2016). - DOI
1. 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). - DOI
1. Zhang, R. et al. Chemical mapping of a single molecule by plasmon-enhanced Raman scattering. Nature 498, 82–86 (2013). - DOI

LinkOut - more resources

Full Text Sources
- Nature Publishing Group

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

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

[3] 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). - DOI

[4] 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). - DOI

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

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

[7] 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). - DOI

[8] 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). - DOI

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

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

Save citation to file

Email citation

Add to Collections

Add to My Bibliography

Your saved search

Create a file for external citation management software

Your RSS Feed

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

Affiliations

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

Authors

Affiliations

Abstract

Comment in

Similar articles

Cited by

References

LinkOut - more resources

Full Text Sources