Abstract
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 language | English |
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Pages (from-to) | 7344-7348 |
Number of pages | 5 |
Journal | ACS Nano |
Volume | 4 |
Issue number | 12 |
Early online date | 18 Oct 2010 |
DOIs | |
Publication status | Published - 28 Dec 2010 |