A New Mechanism of Atomic Manipulation: Bond-Selective Molecular Dissociation <i>via</i> Thermally Activated Electron Attachment

Sakulsermsuk, Sumet; Sloan, Peter; Palmer, Richard E.

doi:10.1021/nn101468e

Cited by 25 publications

(43 citation statements)

References 36 publications

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“…While the physisorption energy agreed quite well with the experiment at that time (see Ref. [7] and references therein), the chemisorption energy seemed to be too high compared to 1.0 eV derived from thermal desorption spectra [26] assuming first-order kinetics and a pre-exponential factor of 10 13 s −1 . Also, periodic DFT calculations [22] using a 2×2 mimic surface reported 1.2 eV chemisorption energy.…”

Section: Introductionsupporting

confidence: 76%

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Local resonances in STM manipulation of chlorobenzene on Si(111)-7×7: performance of different cluster models and density functionals

Utecht

Klamroth

2018

Molecular Physics

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Hot localised charge carriers on the Si(111)-7×7 surface are modelled by small charged clusters. Such resonances induce non-local desorption, i.e. more than 10 nm away from the injection site, of chlorobenzene in scanning tunnelling microscope experiments. We used such a cluster model to characterise resonance localisation and vibrational activation for positive and negative resonances recently. In this work, we investigate to which extent the model depends on details of the used cluster or quantum chemistry methods and try to identify the smallest possible cluster suitable for a description of the neutral surface and the ion resonances. Furthermore, a detailed analysis for different chemisorption orientations is performed. While some properties, as estimates of the resonance energy or absolute values for atomic changes, show such a dependency, the main findings are very robust with respect to changes in the model and/or the chemisorption geometry.

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Section: Introductionsupporting

confidence: 76%

“…the breaking of DNA strands [6]. Therefore, a lot of elementary reaction steps like dissociation [7], desorption [8], bond formation [9] and the switching of molecules [10][11][12] between metastable states have been studied with and induced by STM.…”

Section: Introductionmentioning

confidence: 99%

Local resonances in STM manipulation of chlorobenzene on Si(111)-7×7: performance of different cluster models and density functionals

Utecht

Klamroth

2018

Molecular Physics

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“…Electron-induced surface chlorination of silicon by chlorobenzene has been studied in detail by Palmer, Sloan, and co-workers who showed that, though LAR and directed C−X bond-rupture were prevalent near threshold, the spread in distance and direction of the reacting Cl increased with increasing energy. 13,14 Similar considerations might suggest that localization of reaction would dominate even at metal surfaces, which are much smoother than a semiconductor. The evidence has until now been sparse.…”

Section: ■ Introductionmentioning

confidence: 88%

Localized Reaction at a Smooth Metal Surface: p-Diiodobenzene at Cu(110)

et al. 2012

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Halogenation at a semiconductor surface follows simple dynamics characterized by "localized reaction" along the direction of the halide bond being broken. Here we extend the study of halide reaction dynamics to the important environment of a smooth metal surface, where greater product mobility would be expected. Extensive examination of the physisorbed reagent and chemisorbed products from two successive electron-induced reactions showed, surprisingly, that for this system product localization and directionality described the dynamics at a metal. The reagent was p-diiodobenzene on Cu(110) at 4.6 K. The first C-I bond-breaking yielded chemisorbed iodophenyl and I-atom(#1), and the second yielded phenylene and I-atom(#2). The observed collinear reaction resulted in secondary encounters among products, which revealed the existence of a surface-aligned reaction. The molecular dynamics were well explained by a model embodying a transition between an a priori ground state and a semiempirical ionic state, which can be generally applied to electron-induced chemical reactions at surfaces.

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“…The background to our encounter with non‐local manipulation was a systematic atomic manipulation study of chlorobenzene chemisorbed on the Si(111)‐7×7 surface, which showed a diversity of reactions induced by the scanning tunnelling microscope (STM) tunnelling current, including desorption, diffusion, and C–Cl dissociation. We found, for example, that scanning the silicon surface at low voltage (below +1 V sample bias) had no effect on the molecules, but increasing the STM bias to +2.2 V resulted in chlorobenzene desorption, and proved that this was due to the tunnelling current .…”

Section: Introductionmentioning

confidence: 99%

Non‐Local Atomic Manipulation on Semiconductor Surfaces in the STM: The Case of Chlorobenzene on Si(111)‐7×7

Pan

Sloan

Palmer

2014

The Chemical Record

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Control over individual atoms with the scanning tunnelling microscope (STM) holds the tantalising prospect of atomic-scale construction, but is limited by its "one atom at a time" serial nature. "Remote control" through non-local STM manipulation-as we have demonstrated in the case of chlorobenzene on Si(111)-7×7-offers a new avenue for future "bottom-up" nanofabrication, since hundreds of chemical reactions may be carried out in parallel. Thus a good understanding of the non-local manipulation process, as provided by recent experiments, is important. Comparison of scanning tunnelling spectroscopy (STS) measurements of the bare Si(111)-7×7 surface and chemisorbed chlorobenzene molecules with the voltage dependence of the non-local STM-induced desorption of chlorobenzene proves particularly instructive. For example, the chlorobenzene LUMO appears at +0.9 V with respect to the Fermi level, whereas non-local manipulation thresholds are found at +2.1 V and +2.7 V. This difference supports a picture in which the voltage thresholds for non-local electron-induced desorption depend principally on the energies of the electronic states of the surface. Furthermore, the demonstration that the non-local process is largely insensitive to surface steps up to five layers in height suggests that either the electron transport in this process is subsurface in character or surface charge transport is responsible but is in some way unaffected by the steps.

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A New Mechanism of Atomic Manipulation: Bond-Selective Molecular Dissociation via Thermally Activated Electron Attachment

Cited by 25 publications

References 36 publications

Local resonances in STM manipulation of chlorobenzene on Si(111)-7×7: performance of different cluster models and density functionals

Local resonances in STM manipulation of chlorobenzene on Si(111)-7×7: performance of different cluster models and density functionals

Localized Reaction at a Smooth Metal Surface: p-Diiodobenzene at Cu(110)

Non‐Local Atomic Manipulation on Semiconductor Surfaces in the STM: The Case of Chlorobenzene on Si(111)‐7×7

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