Chemisorption of acrylonitrile on the Cu(100) surface: A local density functional study

Crispin, Xavier; Bureau, Christophe; Geskin, Victor; Lazzaroni, Roberto; Salaneck, W. R.; Brédas, Jean‐Luc

doi:10.1063/1.479604

Cited by 41 publications

(55 citation statements)

References 79 publications

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“…Only the modes relevant to this work are reported. Experimental results for the isolated molecule are taken from [8]. The most striking feature comparing with the results of Tao et al is that, in our calculations, the total energy for the cycloaddition of the cyano group is about 18 kcal·mol −1 (1.08 eV) above the total energy of vertical cycloaddition by the two terminal atoms, while in [1] the former total energy is ∼3-6 kcal·mol −1 below the second one.…”

Section: Resultssupporting

confidence: 75%

A theoretical study of acrylonitrile adsorption on Si(001)

León-Pérez¹,

Miotto²,

Ferraz³

2004

Braz. J. Phys.

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The present work is a comparative study of possible adsorption structures of the conjugated molecule acrylonitrile on Si(001) employing the state of the art pseudopotential method, within a generalized gradient approximation to the density functional theory. In the recent literature it is proposed the interaction of acrylonitrile with Si(001) through a cycloaddition reaction of the cyano group, in competition with the bounding of the two outer atoms of the molecule skeleton with the Si dimer in cross-dimer and cross-trench geometries; between other geometries like which correspond the reaction of the C = C bond with a Si dimer. Starting from a large number of configurations our calculations favor the planar cycloaddition through the terminal N and C atoms on the Si dimer. In this way we explain the electronic and vibrational features obtained experimentally.

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Section: Resultssupporting

confidence: 75%

A theoretical study of acrylonitrile adsorption on Si(001)

León-Pérez¹,

Miotto²,

Ferraz³

2004

Braz. J. Phys.

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“…The greater degree of molecular fragmentation resulting from the chemisorption reaction on iron as compared to noble metals may be attributed to the fact that in addition to catalyzing the reduction reactions, the iron also serves as the electron donor. Because of the higher electronic chemical potential (40) of Fe (−4.02 eV), as compared to a noble metal, such as Pd (−4.75 eV), equalization of the electronic chemical potentials between the adsorbate and the metal result in greater charge transfer in the iron complexes as compared to those with noble metals (33). DFT calculations of di-sigma TCE complexes on a Pd-Cu alloy show that the maximum activation in the C-Cl bonds is only 0.17 Å, and that the three Cl atoms are removed sequentially.…”

Section: Resultsmentioning

confidence: 99%

Understanding Trichloroethylene Chemisorption to Iron Surfaces Using Density Functional Theory

Zhang

Luo

Blowers

et al. 2008

Environ. Sci. Technol.

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This research investigated the thermodynamic favorability and resulting structures for chemical adsorption of trichloroethylene (TCE) to metallic iron using periodic density functional theory (DFT). Three initial TCE positions having the plane defined by HCC atoms parallel to the iron surface resulted in formation of three different chemisorption complexes between carbon atoms in TCE and the iron surface. The Cl-bridge initial configuration with the HCC plane of the TCE molecule perpendicular to the iron surface did not result in C-Fe bond formation. The most energetically favorable complex formed at the C-bridge site where the initial configuration had the C=C bond in TCE at a bridge site between adjacent iron atoms. In the C-bridge complex one C atom formed two sigma bonds to different Fe atoms while the second C atom formed a sigma bond with a second Fe atom. Surface complexation at the C-bridge site resulted in scission of all three C-Cl bonds, and also resulted in a shortening of the C=C bond to a distance intermediate between a double and a triple bond. Initial configurations with the C=C bond adsorbed at top or hollow sites on the iron surface resulted in formation of C-Fe sigma bonds between a single C and two adjacent Fe atoms, and the scission of only two C-Cl bonds. Bond angles and bond lengths indicated that there were no changes in bond order of the C=C bond for top and hollow adsorption. Chemisorption at the C-bridge site had an early transition state in which all three C-Cl bonds were activated from ~1.7 to ~2.2 Å, with an activation energy of 49 kJ/mol. The early transition state and the loss of all three Cl atoms upon chemisorption are consistent with most experimental observations that TCE undergoes complete dechlorination in one interaction with the iron surface. The absence of chemisorption and scission of only two C-Cl bonds at the Cl-bridge site is consistent with experimental observations that trace amounts of chloroacetylene may also be produced from reactions of TCE with iron.

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“…However, this ID does not really exist at the interface, because in fact only the SD of the clean metal surface has been reduced to SD' due to the "push-back effect" (also known as "cushion effect" or Pauli repulsion in the literature); the adsorption of the organic molecule pushes back the electron density of the metal surface that was spilling out into vacuum. The exact change in total electron density distribution at the organic-metal interface can be rather complex, [26][27][28][29] in particular if strong chemical interactions occur, [30,31] and thus depends strongly on the type of molecule and metal. Schematic energy levels at an organic-metal interface with weak interaction (physisorption) "before" and "after" contact, showing that in this case the interface dipole "ID" is a virtual quantity that corresponds to ID = SDÀSD' = fÀf'.…”

Section: Optimizing the Ratio Of Injected Electrons And Holesmentioning

confidence: 99%

Organic Electronic Devices and Their Functional Interfaces

2007

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A most appealing feature of the development of (opto)electronic devices based on conjugated organic materials is the highly visible link between fundamental research and technological advances. Improved understanding of organic material properties can often instantly be implemented in novel device architectures, which results in rapid progress in the performance and functionality of devices. An essential ingredient for this success is the strong interdisciplinary nature of the field of organic electronics, which brings together experts in chemistry, physics, and engineering, thus softening or even removing traditional boundaries between the disciplines. Naturally, a thorough comprehension of all properties of organic insulators, semiconductors, and conductors is the goal of current efforts. Furthermore, interfaces between dissimilar materials-organic/organic and organic/inorganic-are inherent in organic electronic devices. It has been recognized that these interfaces are a key for device function and efficiency, and detailed investigations of interface physics and chemistry are at the focus of research. Ultimately, a comprehensive understanding of phenomena at interfaces with organic materials will improve the rational design of highly functional organic electronic devices.

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Chemisorption of acrylonitrile on the Cu(100) surface: A local density functional study

Cited by 41 publications

References 79 publications

A theoretical study of acrylonitrile adsorption on Si(001)

A theoretical study of acrylonitrile adsorption on Si(001)

Understanding Trichloroethylene Chemisorption to Iron Surfaces Using Density Functional Theory

Organic Electronic Devices and Their Functional Interfaces

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