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Evidence of exciton-libron coupling in chirally adsorbed single molecules

Author

Listed:
  • Jiří Doležal

    (Czech Academy of Sciences
    Charles University)

  • Sofia Canola

    (Czech Academy of Sciences)

  • Prokop Hapala

    (Czech Academy of Sciences)

  • Rodrigo Cezar Campos Ferreira

    (Czech Academy of Sciences)

  • Pablo Merino

    (CSIC and BIST, Campus UAB, Bellaterra
    Instituto de Ciencia de Materiales de Madrid; CSIC)

  • Martin Švec

    (Czech Academy of Sciences
    Czech Academy of Sciences)

Abstract

Interplay between motion of nuclei and excitations has an important role in molecular photophysics of natural and artificial structures. Here we provide a detailed analysis of coupling between quantized librational modes (librons) and charged excited states (trions) on single phthalocyanine dyes adsorbed on a surface. By means of tip-induced electroluminescence performed with a scanning probe microscope, we identify libronic signatures in spectra of chirally adsorbed phthalocyanines and find that these signatures are absent from spectra of symmetrically adsorbed species. We create a model of the libronic coupling based on the Franck-Condon principle to simulate the spectral features. Experimentally measured librational spectra match very well the theoretically calculated librational eigenenergies and peak intensities (Franck-Condon factors). Moreover, the comparison reveals an unexpected depopulation channel for the zero libron of the excited state that can be effectively controlled by tuning the size of the nanocavity. Our results showcase the possibility of characterizing the dynamics of molecules by their low-energy molecular modes using µeV-resolved tip-enhanced spectroscopy.

Suggested Citation

  • Jiří Doležal & Sofia Canola & Prokop Hapala & Rodrigo Cezar Campos Ferreira & Pablo Merino & Martin Švec, 2022. "Evidence of exciton-libron coupling in chirally adsorbed single molecules," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-33653-7
    DOI: 10.1038/s41467-022-33653-7
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    References listed on IDEAS

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