Resolving sub-angstrom ambient motion through reconstruction from vibrational spectra

Jack Griffiths, Tamás Földes, Bart de Nijs*, Rohit Chikkaraddy, Demelza Wright, William M. Deacon, Dénes Berta, Charlie Readman, David Benjamin Grys, Edina Rosta, Jeremy J. Baumberg

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

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Metal/organic-molecule interactions underpin many key chemistries but occur on sub-nm scales where nanoscale visualisation techniques tend to average over heterogeneous distributions. Single molecule imaging techniques at the atomic scale have found it challenging to track chemical behaviour under ambient conditions. Surface-enhanced Raman spectroscopy can optically monitor the vibrations of single molecules but understanding is limited by the complexity of spectra and mismatch between theory and experiment. We demonstrate that spectra from an optically generated metallic adatom near a molecule of interest can be inverted into dynamic sub-Å metal-molecule interactions using a comprehensive model, revealing anomalous diffusion of a single atom. Transient metal-organic coordination bonds chemically perturb molecular functional groups > 10 bonds away. With continuous improvements in computational methods for modelling large and complex molecular systems, this technique will become increasingly applicable to accurately tracking more complex chemistries.

Original languageEnglish
Article number6759
JournalNature Communications
Issue number1
Early online date19 Nov 2021
Publication statusPublished - Dec 2021

Bibliographical note

Funding Information:
We acknowledge financial support from EPSRC grant EP/G060649/1 (J.J.B.), EP/ L027151/1 (J.J.B.), EP/G037221/1 (J.J.B.), EP/R013012/1 (J.J.B.), EPSRC NanoDTC EP/L015978/1 (J.J.B.), and EU grants THOR 829067 and PICOFORCE 883703 (J.J.B.) and ERC starting grant BioNet 757850 (E.R.). B.d.N. acknowledges support from the Leverhulme Trust and Isaac Newton Trust. We acknowledge the use of the Rosalind computing facility at King’s College London. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC EP/P020194/1 (E.R.).

Publisher Copyright:
© 2021, The Author(s).

ASJC Scopus subject areas

  • Chemistry(all)
  • Biochemistry, Genetics and Molecular Biology(all)
  • Physics and Astronomy(all)


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