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Charge-Induced Structural Changes in a Single Molecule Investigated by Atomic Force Microscopy.

Philipp Scheuerer1, Laerte L Patera1, Felix Simbürger1

  • 1Institute of Experimental and Applied Physics, University of Regensburg, 93053 Regensburg, Germany.

Physical Review Letters
|September 7, 2019
PubMed
Summary
This summary is machine-generated.

Structural changes in single copper(II)phthalocyanine (CuPc) molecules upon electron transfer were measured using atomic force microscopy (AFM). These subangstrom relaxations, crucial for redox reactions, were linked to electrostatic interactions with the surface.

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Area of Science:

  • Surface Science
  • Physical Chemistry
  • Nanotechnology

Background:

  • Electron transfer is fundamental to redox reactions.
  • Understanding molecular structural changes upon charging is key to controlling reaction rates.
  • Atomic Force Microscopy (AFM) offers high-resolution imaging capabilities.

Purpose of the Study:

  • To quantify subangstrom structural changes in single copper(II)phthalocyanine (CuPc) molecules upon single-electron charging.
  • To correlate these structural changes with electron transfer events.
  • To investigate the role of electrostatic interactions in molecular relaxations.

Main Methods:

  • Atomically resolved atomic force microscopy (AFM) was employed.
  • Single copper(II)phthalocyanine (CuPc) molecules were deposited on an ultrathin NaCl film.
  • Molecules were imaged in both neutral and anionic charge states.
  • Density functional theory (DFT) simulations were used for comparison.

Main Results:

  • Distinct differences in AFM contrast were observed between neutral and anionic CuPc molecules.
  • These contrast changes directly correspond to geometric structure relaxations upon charging.
  • A significant contribution from nonhomogeneous vertical relaxation was identified.
  • This relaxation is driven by altered electrostatic interactions with the substrate.

Conclusions:

  • Subangstrom structural dynamics of single molecules can be precisely measured using AFM.
  • Electron transfer induces significant molecular relaxations, impacting redox reaction rates.
  • Electrostatic forces play a dominant role in mediating these structural changes.