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.