Mechanisms of Halogen-Based Covalent Self-Assembly on Metal Surfaces

Björk, Jonas; Hanke, Felix; Stafström, Sven

doi:10.1021/ja400304b

Cited by 238 publications

(423 citation statements)

References 38 publications

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“…[1][2][3][4][5] These apparently contradictory properties of the same material are at the heart of an active research field in current surface science. While pristine Au surfaces are unable to dissociate hydrogen and oxygen molecules, 2,6 they significantly lower the temperature for dehalogenation reactions that are an important step in the assembly of covalently bonded molecular nanostructures [7][8][9][10][11] and graphene nanoribbons. 12,13 To modify chemical bonds bonds in these surface science applications, one requires a relatively chemically inert surface to which large molecules adhere primarily through noncovalent van der Waals interactions, yet one that is reactive enough to cleave only a few bonds.…”

Section: Introductionmentioning

confidence: 99%

Structure and local reactivity of the Au(111) surface reconstruction

2013

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The close-packed (111) surface of gold is well known to show a 22 × √ 3 reconstruction on single nm lengths with a long-range herringbone pattern on scales of a few hundred nm. Here we investigate the local reconstruction using density functional theory and compare the results to scanning tunneling microscopy experiments. Moreover, we use hydrogen and fluorine as probe atoms to investigate changes in the ability of the Au(111) surface to catalyze the reactions involved in the formation of molecular nanostructures. We find a small variation of the reactivity across different surface sites and link those results to the local coordination environment of the face-centered-cubic (fcc), hexagonal-close-packed (hcp), and ridge regions. Finally, we scrutinize a commonly used approximation in density functional studies, namely that Au (111) is atomically flat and a perfect termination of the fcc lattice.

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Section: Introductionmentioning

confidence: 99%

Structure and local reactivity of the Au(111) surface reconstruction

2013

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“…Furthermore, previous investigations of other interfacial covalent assembly schemes 14,[21][22][23][24] Ag(111)…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Mechanism of the Covalent Coupling Between Terminal Alkynes on a Noble Metal

et al. 2014

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The mechanism of the newly reported route for surface-assisted covalent coupling of terminal alkynes on Ag(111) is unraveled by density functional theory based transition state calculations. We illustrate that the reaction path is fundamentally different from the classical coupling schemes in wet chemistry. It is initiated by the covalent coupling between two molecules instead of single-molecule dehydrogenation. The silver substrate is found to play an important role stabilizing the intermediate species by chemical bonds, although it is hardly active electronically in the actual coupling step. The dimer intermediate is concluded to undergo two subsequent dehydrogenation processes expected to be rate-limiting according to the comparatively large barriers, which origin is discussed.

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“…11,[15][16][17][18][19][20][21][22][23] These studies have almost exclusively been performed at 0 K, excluding even zero-point vibrations, and only a few examples have attempted to include temperature effects. 11,20 In particular, no studies have addressed the thermodynamics of reactions related to on-surface synthesis.…”

Section: 5mentioning

confidence: 99%

Thermodynamics of an Electrocyclic Ring-Closure Reaction on Au(111)

Björk

2016

J. Phys. Chem. C

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We have computationally studied the effects of temperature on the reaction pathway of an electrocyclic ring-closure reaction on the Au(111) surface, particularly focusing on thermodynamic aspects of the reaction. The electrocyclic ring-closure is accompanied by a series of dehydrogenation steps, and while it is found that temperature, in terms of vibrational entropy and enthalpy, has a reducing effect on most energy barriers, it does not alter the qualitative appreciation of the reaction kinetics. However, it is found that the way the abstracted hydrogen atoms are treated is crucial for the thermodynamics of the reaction. The overall reaction is highly endothermic, but becomes thermodynamically favorable due to the entropy gain of the hydrogen byproducts, which desorb associatively from the surface as H 2 . The study provides new outlooks for the theoretical treatment of reactions related to on-surface synthesis, anticipated to be instructive for future studies.

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Mechanisms of Halogen-Based Covalent Self-Assembly on Metal Surfaces

Cited by 238 publications

References 38 publications

Structure and local reactivity of the Au(111) surface reconstruction

Structure and local reactivity of the Au(111) surface reconstruction

Unraveling the Mechanism of the Covalent Coupling Between Terminal Alkynes on a Noble Metal

Thermodynamics of an Electrocyclic Ring-Closure Reaction on Au(111)

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