10.1021/nn101468e.s001
Sumet Sakulsermsuk
Sumet
Sakulsermsuk
Peter A. Sloan
Peter A.
Sloan
Richard E. Palmer
Richard E.
Palmer
A New Mechanism of Atomic Manipulation: Bond-Selective Molecular Dissociation <i>via</i> Thermally Activated Electron Attachment
American Chemical Society
2010
chlorobenzene molecules chemisorbed
electron beam
surface systems
Thermal excitation
dissociation
Thermally Activated Electron AttachmentWe report
mechanism
New Mechanism
physisorbed precursor states
STM manipulation
Atomic Manipulation
target molecule
energy barrier
room temperature
scanning tunneling microscope
2010-12-28 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/A_New_Mechanism_of_Atomic_Manipulation_Bond_Selective_Molecular_Dissociation_i_via_i_Thermally_Activated_Electron_Attachment/2702134
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)-7 × 7 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.