Real-space adsorption studies of cyclooctyne on Si(001)

Mette, Gerson; Dürr, Michael; Bartholomäus, Ruben; Koert, Ulrich; Höfer, U.

doi:10.1016/j.cplett.2012.11.029

Cited by 27 publications

(46 citation statements)

References 39 publications

(45 reference statements)

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“…While these two examples have illustrated cases where Pauli repulsion is limiting the adsorption at high coverages, there are also systems where coverage effects are driven by other forces: In the adsorption of cyclooctyne on Si(001), the formation of chain‐like structures is observed at medium coverages . Using pEDA and other computational methods, we could show that Pauli repulsion is not the determining factor in the emergence of this phenomenon.…”

Section: Chemical Bonding At Surfacesmentioning

confidence: 99%

Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Pecher

Tonner

2018

WIREs Comput Mol Sci

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Chemical bonding concepts like covalency, ionicity, Pauli repulsion, shared-electron, or donor-acceptor bonding are important tools to sort our vast knowledge in chemistry and predict new reactivity. Electronic structure analysis provides the basis for a detailed understanding of the origins of these concepts. Energy decomposition analysis (EDA) is an established method for molecules and has recently been implemented for application in extended systems, that is, surfaces and solids, where it is termed periodic EDA (pEDA). The foundations and applications of this method which enables the derivation of bonding concepts are outlined in this review. Embedded in key examples from molecular and solid-state chemistry, the major part covers the adsorption and reactivity of molecules with surfaces with a focus on organic molecules interacting with semiconductor surfaces. Based on electronic structure analysis and supported by a quantitative methodology, we show that analogous bonding concepts can be applied in diverse chemical environments. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Structure and Mechanism > Computational Materials Science K E Y W O R D S chemical bonding, density functional theory, energy decomposition analysis, surface chemistry 1 | INTRODUCTIONThe chemical bond is the central concept in the discussion of structures and reactivity in chemistry. The nature of the forces that hold atoms together thrills chemists since the upcoming of atomistic theories. First realistic models were derived more than two centuries ago based on experimental observations. 1 The paradigm shift at the beginning of the 20th century then provided the basis for our present-day understanding of chemical bonding in terms of quantum mechanical principles. 2,3 But by no means did this development end the discussion about chemical bonding and the interpretation of results obtained by theory and computation. The intrinsic ambiguity in discussing often nonobservable properties that are connected to very useful concepts like covalency, ionicity, Pauli repulsion, bond order, and alike fosters the scientific discussion and leads to a further refinement of our understanding of the chemical bond. [4][5][6][7][8][9][10][11] The development of bonding concepts in molecular and solid-state chemistry evolved separately for the most part. For molecules, the view on (more or less) localized bonds as given by the Lewis picture more than a century ago 12 was regained both by valence bond (VB) theory and from the molecular orbital (MO) approach by the linear combination of atomic orbitals (LCAO) and localization procedures. [13][14][15][16] This resulted in the development of many powerful methods for electronic structure analysis for the qualitative and quantitative interpretation of chemical bonding that have been summarized in previous reviews. 2,17-21 Some examples will be discussed in the next section. In the field of surfaces and solids, the delocalized view

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Section: Chemical Bonding At Surfacesmentioning

confidence: 99%

Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Pecher

Tonner

2018

WIREs Comput Mol Sci

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“…Therefore, the adsorption monolayer of simple saturated hydrocarbons on Si(001)-2 × 1 has low thermal stability and, consequently, is not interesting from the practical point of view. On the other hand, the main result of the recent studies is the finding that a hydrocarbon molecule containing several unsaturated bonds can have several adsorption configurations differing in the number of di-σ bonds formed between the adsorbed molecules and the silicon surface [5,[8][9][10][11][12]. Based on the results of the DFT calculations a stable π-precursor was supposed to be formed due to the interaction between an unsaturated hydrocarbon molecule and a silicon atom (three-membered π-complex precursor) [13].…”

Section: Introductionmentioning

confidence: 98%

“…Later, these π-precursors were observed experimentally [14]. The available experimental data [9][10][11][12][15][16][17][18][19] are ambiguous and, therefore, most of the theoretical works are focused on the quantum-chemical calculations of binding energies for the different adsorption configurations [5,[19][20][21][22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Modeling of 1,4-cyclohexadiene adsorption thermodynamics on Si(001)-2 × 1 surface

et al. 2015

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“…Cyclooctyne ( 1 ), the smallest stable cyclic alkyne, on Si(001) is a system where this is the case and it has previously been thoroughly studied by experiment and theory [ 6 – 8 ]. Even though 1 is missing a second functional group necessary for the LbL approach, previous studies have shown that synthetic routes exist for derivatization and that the reactivity of the strained triple bond of 1 with the surface is not affected by the second functional group [ 4 – 5 9 ].…”

Section: Introductionmentioning

confidence: 99%

“…Experimental studies in combination with Monte Carlo simulations have shown that growth of 1 on Si(001) results in non-statistical formation of chains with an average distance of 1.5 to 2 dimers between adsorbates [ 6 ]. For the adsorption of methanol on Ge(001), where a similar behaviour is observed, it was shown that in an intermediate state, interactions with other adsorbed molecules lead to a reduction of the energy barrier for conversion into the final chemisorbed state [ 11 ].…”

Section: Introductionmentioning

confidence: 99%

Dispersion-mediated steering of organic adsorbates on a precovered silicon surface

Pecher¹,

Schmidt²,

Tonner³

2018

Beilstein J. Org. Chem.

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The chemistry of organic adsorbates on surfaces is often discussed in terms of Pauli repulsion as limiting factor regarding the packing of molecules. Here we show that the attractive part of the van der Waals potential can be similarly decisive. For the semiconductor surface Si(001), an already covalently bonded molecule of cyclooctyne steers a second incoming molecule via dispersion interactions onto the neighbouring adsorption site. This helps in understanding the nonstatistical pattern formation for this surface–adsorbate system and hints toward an inclusion of dispersion attraction as another determining factor for surface adsorption.

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Real-space adsorption studies of cyclooctyne on Si(001)

Cited by 27 publications

References 39 publications

Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Deriving bonding concepts for molecules, surfaces, and solids with energy decomposition analysis for extended systems

Modeling of 1,4-cyclohexadiene adsorption thermodynamics on Si(001)-2 × 1 surface

Dispersion-mediated steering of organic adsorbates on a precovered silicon surface

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