A new mechanism of atomic manipulation: bond-selective molecular dissociation via thermally activated electron attachment

Sumet Sakulsermsuk, Peter A Sloan, Richard E Palmer

Research output: Contribution to journalArticlepeer-review

21 Citations (Scopus)


We report a new mechanism of (bond-selective) atomic manipulation in the scanning tunneling microscope (STM). We demonstrate a channel for one-electron-induced C-Cl bond dissociation in chlorobenzene molecules chemisorbed on the Si(111)-7x7 surface, at room temperature and above, which is thermally activated. We find an Arrhenius thermal energy barrier to one-electron dissociation of 0.8+-0.2 eV, which we correlate explicitly with the barrier between chemisorbed and physisorbed precursor states of the molecule. Thermal excitation promotes the target molecule from a state where one-electron dissociation is suppressed to a transient state where efficient one-electron dissociation, analogous to the gas-phase negative-ion resonance process, occurs. We expect the mechanism will be obtained in many surface systems, and not just in STM manipulation, but in photon and electron beam stimulated (selective) chemistry.
Original languageEnglish
Pages (from-to)7344-7348
Number of pages5
JournalACS Nano
Issue number12
Early online date18 Oct 2010
Publication statusPublished - 28 Dec 2010

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