Adsorption and reaction of organic molecules on solid surfaces – ab-initio density functional investigations

Häfner, J.

doi:10.1007/s00706-007-0828-6

Cited by 13 publications

(12 citation statements)

References 66 publications

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“…In a recent review, Hafner 15 has discussed the use of ab initio density functional investigations to the adsorption and reaction of organic molecules on solid surfaces. The surface is modeled by a periodic slab geometry.…”

Section: Computational Detailsmentioning

confidence: 99%

Thermodynamic factors limiting the preservation of aromaticity of adsorbed organic compounds on Si(100): Example of the pyridine

Coustel

Carniato

Boureau

2011

The Journal of Chemical Physics

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Using pyridine as an example, a thermodynamic analysis of the low temperatures adsorption of aromatic organic molecules with a N atom on the Si(100) surface is presented. This study is restricted to the case of an equilibrium with the gas phase. Dative attachment which is the only way to preserve aromaticity is the more stable form of adsorbed pyridine in dilute solutions at low temperatures. Two factors limit the domain of stability of dative attachment: repulsive interactions between dative bonds prevent them from being present in concentrated solutions while aromaticity contributes to a decrease in the entropy, which explains the vanishing of dative bonds at high temperatures even in dilute solutions.

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Section: Computational Detailsmentioning

confidence: 99%

Thermodynamic factors limiting the preservation of aromaticity of adsorbed organic compounds on Si(100): Example of the pyridine

Coustel

Carniato

Boureau

2011

The Journal of Chemical Physics

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“…1,2 Likewise quantum chemical calculations, particularly those based on density functional theory (DFT), have advanced to a stage where it is possible to analyze complex reaction pathways and to calculate rate coefficients for elementary processes. [3][4][5][6][7][8] In a number of instances, it has been demonstrated that overall reaction kinetics determined using such rate coefficients correctly describe observed rates and changes with catalyst composition. [9][10][11][12] These successes suggest that by combining different theoretical methods, it should be possible to make quantitative predictions of reaction kinetics for systems involving the combined effects of reaction kinetics, adsorption, and diffusion.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Simulation of n-Alkane Cracking on Zeolites

et al. 2010

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The kinetics of alkane cracking in zeolites MFI and FAU have been simulated theoretically from first principles. The apparent rate coefficient for alkane cracking was described as the product of the number of alkane molecules per unit mass of zeolite that are close enough to a Brønsted-acid site to be in the reactant state for the cleavage of a specific C-C bond and the intrinsic rate coefficient for the cleavage of that bond. Adsorption thermodynamics were calculated by Monte Carlo simulation and the intrinsic rate coefficient for alkane cracking was determined from density functional theory calculations combined with absolute rate theory. The effects of functional, basis set, and cluster size on the intrinsic activation energy for alkane cracking were investigated. The dependence of the apparent rate coefficient on the carbon number for the cracking of C 3 -C 6 alkanes on MFI and FAU determined by simulation agrees well with experimental observation, but the absolute values of the apparent rate coefficients are a factor of 10 to 100 smaller than those observed. This discrepancy is attributed to the use of a small T5 cluster representation of the Brønsted-acid site. Limited calculations for propane and butane cracking on MFI reveal that significantly better agreement between prediction and observation is achieved using a T23 cluster for both the apparent rate coefficient and the apparent activation energy. The apparent rate coefficients for alkane cracking are noticeably larger for MFI than FAU, in agreement with recent findings reported in the experimental literature.

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“…The stepwise hydrogenation of benzene to 1,4-cyclohexadiene (C 6 H 8 ) has been studied theoretically by Mittendorfer & Hafner (2002) and Hafner (2008), who report an activation barrier of 0.73 eV for addition of the first H atom and 0.40 eV for addition of the second; the first reaction is asserted to be the rate-determining step in the full hydrogenation to cyclohexane (C 6 H 12 ), but no further barriers are reported to support this claim (Mittendorfer & Hafner 2002;Hafner 2008).…”

Section: (C) Hydrogenation Of Benzenementioning

confidence: 99%

Aromatic adsorption on metals via first-principles density functional theory

2009

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We review first-principles calculations relevant to the adsorption of aromatic molecules on metal surfaces. Benzene has been intensively studied on a variety of substrates, providing an opportunity to comment upon trends from one metal to another. Meanwhile, calculations elucidating the adsorption of polycyclic aromatic molecules are more sparse, but nevertheless yield important insights into the role of non-covalent interactions. Heterocyclic and substituted aromatic compounds introduce the complicating possibility of electronic and steric effects, whose relative importance can thus far only be gauged on a case-by-case basis. Finally, the coadsorption and/or reaction of aromatic molecules is discussed, highlighting an area where the predictive power of theory is likely to prove decisive in the future.

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Adsorption and reaction of organic molecules on solid surfaces – ab-initio density functional investigations

Cited by 13 publications

References 66 publications

Thermodynamic factors limiting the preservation of aromaticity of adsorbed organic compounds on Si(100): Example of the pyridine

Thermodynamic factors limiting the preservation of aromaticity of adsorbed organic compounds on Si(100): Example of the pyridine

Theoretical Simulation of n-Alkane Cracking on Zeolites

Aromatic adsorption on metals via first-principles density functional theory

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