Single-electron induces double-reaction by charge delocalization

Kai Huang, Lydie Leung, Tingbin Lim, Zhanyu Ning, John C. Polanyi*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

38 Scopus citations


Injecting an electron by scanning tunneling microscope into a molecule physisorbed at a surface can induce dissociative reaction of one adsorbate bond. Here we show experimentally that a single low-energy electron incident on ortho-diiodobenzene physisorbed on Cu(110) preferentially induces reaction of both of the C-I bonds in the adsorbate, with an order-of-magnitude greater efficiency than for comparable cases of single bond breaking. A two-electronic-state model was used to follow the dynamics, first on an anionic potential-energy surface (pes*) and subsequently on the ground state pes. The model led to the conclusion that the two-bond reaction was due to the delocalization of added charge between adjacent halogen-atoms of ortho-diiodobenzene through overlapping antibonding orbitals, in contrast to the cases of para-dihalobenzenes, studied earlier, for which electron-induced reaction severed exclusively a single carbon-halogen bond. The finding that charge delocalization within a single molecule can readily cause concerted two-bond breaking suggests the more general possibility of intra- and also intermolecular charge delocalization resulting in multisite reaction. Intermolecular charge delocalization has recently been proposed by this laboratory to account for reaction in physisorbed molecular chains (Ning, Z.; Polanyi, J. C.Angew. Chem., Int. Ed. 2013, 52, 320-324).

Original languageEnglish
Pages (from-to)6220-6225
Number of pages6
JournalJournal of the American Chemical Society
Issue number16
StatePublished - 24 Apr 2013
Externally publishedYes


Dive into the research topics of 'Single-electron induces double-reaction by charge delocalization'. Together they form a unique fingerprint.

Cite this