Molecular Dynamics of the Electron-Induced Reaction of Diiodomethane on Cu(110)

Chatterjee, Avisek; Cheng, Fang; Leung, Lydie; Luo, Meng‐Bo; Ning, Zhanyu; Polanyi, J. C.

doi:10.1021/jp508014x

Cited by 11 publications

(19 citation statements)

References 25 publications

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“…Both I atoms recoil along the initial C–I bond directions, as observed experimentally, since two-bond dissociation occurs in a time short compared with molecular rotation. A similar mechanism of concerted reaction by single electron impact was reported previously for CH 2 I 2 on Cu(110), in which the I2S model predicted that the first C–I bond would break promptly, and the second ∼0.5 ps later due to internal excitation of the CH 2 I fragment …”

Section: Resultssupporting

confidence: 73%

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Clocking Surface Reaction by In-Plane Product Rotation

et al. 2016

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Electron-induced reaction of physisorbed meta-diiodobenzene (mDIB) on Cu(110) at 4.6 K was studied by Scanning Tunneling Microscopy and molecular dynamics theory. Single-electron dissociation of the first C-I bond led to in-plane rotation of an iodophenyl (IPh) intermediate, whose motion could be treated as a "clock" of the reaction dynamics. Alternative reaction mechanisms, successive and concerted, were observed giving different product distributions. In the successive mechanism, two electrons successively broke single C-I bonds; the first C-I bond breaking yielded IPh that rotated directionally by three different angles, with the second C-I bond breaking giving chemisorbed I atoms (#2) at three preferred locations corresponding to the C-I bond alignments in the prior rotated IPh configurations. In the concerted mechanism a single electron broke two C-I bonds, giving two chemisorbed I atoms; significantly these were found at angles corresponding to the C-I bond direction for unrotated mDIB. Molecular dynamics accounted for the difference in reaction outcomes between the successive and the concerted mechanisms in terms of the time required for the IPh to rotate in-plane; in successive reaction the time delay between first and second C-I bond-breaking events allowed the IPh to rotate, whereas in concerted reaction the computed delay between excitation and reaction (∼1 ps) was too short for molecular rotation before the second C-I bond broke. The dependence of the extent of motion at a surface on the delay between first and second bond breaking suggested a novel means to "clock" sub-picosecond dynamics by imaging the products arising from varying time delays between impacting pairs of electrons.

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Section: Resultssupporting

confidence: 73%

“…A similar mechanism of concerted reaction by single electron impact was reported previously for CH 2 I 2 on Cu(110), in which the I2S model predicted that the first C−I bond would break promptly, and the second ∼0.5 ps later due to internal excitation of the CH 2 I fragment. 38 2.5. Time-Resolved Dynamics.…”

Section: Resultsmentioning

confidence: 99%

Clocking Surface Reaction by In-Plane Product Rotation

et al. 2016

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“…A number of experiments explore the reaction path and kinetics of dissociative reactions of haloalkanes and haloarenes on Cu(110). − The STM can be used to follow the adsorbed molecules from the physisorbed (self-assembly) state to chemisorbed (imprinting) state. In the case of p -diiodobenzene, the initial separation of the two terminal iodine atoms of the monomer, dimer, or trimer assembly imprints the final product.…”

Section: On-surface Reactionsmentioning

confidence: 99%

Supramolecular Assemblies on Surfaces: Nanopatterning, Functionality, and Reactivity

et al. 2018

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Understanding how molecules interact to form large-scale hierarchical structures on surfaces holds promise for building designer nanoscale constructs with defined chemical and physical properties. Here, we describe early advances in this field and highlight upcoming opportunities and challenges. Both direct intermolecular interactions and those that are mediated by coordinated metal centers or substrates are discussed. These interactions can be additive, but they can also interfere with each other, leading to new assemblies in which electrical potentials vary at distances much larger than those of typical chemical interactions. Earlier spectroscopic and surface measurements have provided partial information on such interfacial effects. In the interim, scanning probe microscopies have assumed defining roles in the field of molecular organization on surfaces, delivering deeper understanding of interactions, structures, and local potentials. Self-assembly is a key strategy to form extended structures on surfaces, advancing nanolithography into the chemical dimension and providing simultaneous control at multiple scales. In parallel, the emergence of graphene and the resulting impetus to explore 2D materials have broadened the field, as surface-confined reactions of molecular building blocks provide access to such materials as 2D polymers and graphene nanoribbons. In this Review, we describe recent advances and point out promising directions that will lead to even greater and more robust capabilities to exploit designer surfaces.

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“…[8][9][10]12,13 The higher reaction yield of 10 −7 was previously reported for one case, the electron-induced dissociation of CH 2 I 2 adsorbed on Cu(110), being ascribed in that work to the weak C−I bond. 14 The present study suggests that the cause may be weaker coupling of aliphatic reagent than aromatic reagent to the metallic substrate, with consequent longer lifetime of the aliphatic anion, hence more efficient dissociation. Comparison with earlier work (see below) suggests that this contrasting behavior applies more generally, enhancing the efficiency of electron-induced reaction of aliphatics as compared with aromatics.…”

Section: Introductionmentioning

confidence: 70%

Contrasting Efficiency of Electron-Induced Reaction at Cu(110) in Aliphatic and Aromatic Bromides

et al. 2020

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We report a comparative study of the electron-induced reaction of pentyl bromide (PeBr) and phenyl bromide (PhBr) on Cu(110) at 4.6 K, observed by scanning tunneling microscopy (STM). The induced dissociation of the intact adsorbed molecule for both reagents occurred at an energy of 2.0 eV, producing a hydrocarbon radical and a Br atom. Electron-induced C–Br bond dissociation was found to be a single-electron process for both reagents. The impulsive two-state (I2S) model was used to describe the Br atom recoil as due to molecular excitation to a repulsive anti-bonding state, in which recoil of the dissociation products occurred due to C·Br repulsion along the prior C–Br bond direction. The measured reaction yield was 3 orders of magnitude greater for PeBr, 2.0 × 10–7 reactive events per electron, than for PhBr with a yield of 1.7 × 10–10. The low yield of dissociation products from the aromatic PhBr was attributed to the presence of two additional anionic states below the 2.0 eV energy limit, absent for the aliphatic PeBr; these additional anionic states for PhBr could provide a pathway for electron transfer to the surface in the case of the aromatic, but not the aliphatic, anion. The consequent shorter lifetime of the repulsive aromatic anion of PhBr is consistent with the observation of shorter mean recoil distance (3.2 Å) of its Br dissociation product, as compared with the markedly longer recoil (8.7 Å) of Br observed from the anion of PeBr.

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Molecular Dynamics of the Electron-Induced Reaction of Diiodomethane on Cu(110)

Cited by 11 publications

References 25 publications

Clocking Surface Reaction by In-Plane Product Rotation

Clocking Surface Reaction by In-Plane Product Rotation

Supramolecular Assemblies on Surfaces: Nanopatterning, Functionality, and Reactivity

Contrasting Efficiency of Electron-Induced Reaction at Cu(110) in Aliphatic and Aromatic Bromides

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