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Evidence for Ultralow-Energy Vibrations in Large Organic Molecules

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Institute of Physics & University of Chinese Academy of Sciences, Chinese Academy of Sciences, P.O. Box 603, Beijing 100190, China
School of Chemistry, Newcastle University, Newcastle upon Tyne NE1 7RU, United Kingdom
§ Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
Department of Physics and Astronomy and Department of Electrical Engineering and Computer Science, Vanderbilt University, Nashville, Tennessee 37235, United States
Cite this: Nano Lett. 2017, 17, 8, 4929–4933
Publication Date (Web):July 20, 2017
https://doi.org/10.1021/acs.nanolett.7b01963
Copyright © 2017 American Chemical Society
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Abstract

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The quantum efficiency or the rate of conversion of incident photon to free electron in photosynthesis is known to be extremely high. It has long been thought that the origin of this efficiency are molecular vibrations leading to a very fast separation of electrons and holes within the involved molecules. However, molecular vibrations are commonly in the range above 100 meV, which is too high for excitations in an ambient environment. Here, we analyze experimental spectra of single organic molecules on metal surfaces at ∼4 K, which often exhibit a pronounced dip. We show that measurements on iron(II) [tetra-(pentafluorophenyl)]porphyrin resolve this single dip at 4 K into a series of step-shaped inelastic excitations at 0.4 K. Via extensive spectral maps under applied magnetic fields and corresponding theoretical analysis we find that the dip is due to ultralow-energy vibrations of the molecular frame, typically in the range below 20 meV. The result indicates that ultralow energy vibrations in organic molecules are much more common than currently thought and may be all-pervasive for molecules above a certain size.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.nanolett.7b01963.

  • Additional information on the on-surface dechlorination reactions of FeF20TPPCl and self-assembly of FeF20TPP, molecular orbitals of FeF20TPP with different azimuthal orientation on Au(111), IETS taken on central Fe2+ ion with increasing magnetic field and on the molecular frame with increasing magnetic field at 0.4 K (PDF)

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Cited By


This article is cited by 3 publications.

  1. Lei Tao, Yu-Yang Zhang, Sokrates T. Pantelides, Shixuan Du. Tuning the Catalytic Activity of a Quantum Nutcracker for Hydrogen Dissociation. Surfaces 2020, 3 (1) , 40-47. https://doi.org/10.3390/surfaces3010004
  2. Carmen Rubio-Verdú, Ane Sarasola, Deung-Jang Choi, Zsolt Majzik, René Ebeling, M. Reyes Calvo, Miguel M. Ugeda, Aran Garcia-Lekue, Daniel Sánchez-Portal, Jose Ignacio Pascual. Orbital-selective spin excitation of a magnetic porphyrin. Communications Physics 2018, 1 (1) https://doi.org/10.1038/s42005-018-0015-6
  3. Thomas Pope, Shixuan Du, Hong-Jun Gao, Werner A. Hofer. Electronic effects and fundamental physics studied in molecular interfaces. Chemical Communications 2018, 54 (44) , 5508-5517. https://doi.org/10.1039/C8CC02191K

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