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In the region where two bulk phases meet, an intricate electric charge distribution arises due to charge transfer, ion adsorption, molecular orientation, and charge distortion. This complex distribution is commonly referred to as the electrical double layer.When a solid electrode interfaces with ions in an electrolyte solution, the speed of electron transfer dictates the rates of oxidation and reduction. The electrode acquires a charge through the escape of atoms into the solution as cations or...
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Related Experiment Video

Updated: May 12, 2026

All-electronic Nanosecond-resolved Scanning Tunneling Microscopy: Facilitating the Investigation of Single Dopant Charge Dynamics
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Single-electron induces double-reaction by charge delocalization.

Kai Huang1, Lydie Leung, Tingbin Lim

  • 1Lash Miller Chemical Laboratories, Department of Chemistry and Institute of Optical Sciences, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 Canada.

Journal of the American Chemical Society
|April 16, 2013
PubMed
Summary

Electron injection into ortho-diiodobenzene on a copper surface triggers a unique two-bond breaking reaction. This efficient process, driven by charge delocalization, differs from single-bond breaking observed in similar molecules.

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Area of Science:

  • Surface Science
  • Physical Chemistry
  • Quantum Mechanics

Background:

  • Electron-induced reactions on surfaces are crucial for understanding chemical transformations at the molecular level.
  • Previous studies showed single bond breaking in similar molecules upon electron injection.

Purpose of the Study:

  • To investigate the effect of electron injection on ortho-diiodobenzene molecules physisorbed on a Cu(110) surface.
  • To explore the mechanism behind electron-induced bond dissociation in this specific molecular system.

Main Methods:

  • Experimental electron injection using a scanning tunneling microscope (STM).
  • Analysis of reaction dynamics using a two-electronic-state model involving anionic and ground state potential energy surfaces (PES).

Main Results:

  • Single low-energy electron injection preferentially induced the breaking of both carbon-iodine (C-I) bonds in ortho-diiodobenzene.
  • This two-bond reaction occurred with an order-of-magnitude greater efficiency compared to single bond breaking.
  • The enhanced reactivity was attributed to charge delocalization between adjacent iodine atoms via overlapping antibonding orbitals.

Conclusions:

  • Charge delocalization within a single molecule can lead to concerted multi-bond breaking.
  • This finding suggests broader possibilities for intra- and intermolecular charge delocalization driving multisite reactions.
  • Contrasts with para-dihalobenzenes where only single C-X bond cleavage was observed.