The bonding of acrylonitrile molecules to copper surfaces

Loo, B. H.; Kato, Tsuyoshi

doi:10.1016/0039-6028(93)90534-q

Cited by 15 publications

(15 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In the experimental spectrum of Ref. 26, a broad peak at 446 cm Ϫ1 was assigned to AN-Cu bonds, while no useful information could be obtained below 400 cm Ϫ1 . In that frequency range, the calculated spectrum shows two peaks ͑at 220 and 317 cm Ϫ1 ͒ that are characteristic of the Cu-C stretching ͑the first mode involves not only the Cu-C stretching but other atomic displacements as well͒, while the peak at 436 cm Ϫ1 represents the stretching of the Cu-N bond.…”

Section: A Geometric Structure Of An Copper Complexesmentioning

confidence: 96%

“…[23][24][25] On the basis of this argument and since the adsorption geometry of AN does not change with cluster size, the smallest complex, ͓Cu 9 -AN͔, is chosen to estimate the vibrational properties of acrylonitrile adsorbed on copper in order to compare with experimental results. 26 Upon chemisorption, we expect that the appearance of new bonds translates into new features in the vibrational frequency spectrum and modifications of the features related to isolated AN.…”

Section: A Geometric Structure Of An Copper Complexesmentioning

confidence: 99%

“…Figure 2͑b͒ represents the calculated IR spectrum of the ͓Cu 9 -AN͔ complex, which will be compared to the surfaceenhanced Raman ͑SER͒ spectrum of the AN copper interface obtained by Loo and Kato. 26 Since the experimental spectrum is expected to be influenced by the vibrational Stark effect ͑resulting from the electric field due to electrode polarization and the medium effect͒ and the polycrystalline nature of the metal, the comparison with the calculated values can only be semiquantitative.…”

Section: A Geometric Structure Of An Copper Complexesmentioning

confidence: 99%

“…This result is consistent with the fact that acrylonitrile is chemisorbed on the copper surface under UHV conditions, as shown by the XPS data, and in its liquid phase as observed in the experiments by Loo and Kato. 26 The entropic contribution T⌬S ads decreases the strength of chemisorption by Ϫ17.6 kcal/mol at 298 K; the entropic modification is thus far from being negligible in the chemisorption process ͑note that the adsorption free enthalpy of acrylonitrile from solution should be smaller than that from gas phase because of the attractive interaction of the surrounding medium composed of solvent and acrylonitrile 1e ͒.…”

Section: ͑7͒mentioning

confidence: 99%

See 3 more Smart Citations

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

Crispin

Bureau

Geskin

et al. 1999

The Journal of Chemical Physics

View full text Add to dashboard Cite

The possibility of chemically grafting polyacrylonitrile onto transition metal electrodes via electropolymerization leads to promising applications in the fields of corrosion protection or metal surface functionalization. The initial step of the electrografting mechanism is the adsorption of the acrylonitrile monomer on the metal surface from solution. Here, we investigate theoretically this adsorption process on the copper ͑100͒ surface; Density Functional Theory is used in the Local Spin Density approximation to describe the electronic and structural properties of acrylonitrile adsorbed on copper clusters. The chemisorption of acrylonitrile on the copper surface is confirmed experimentally via X-Ray Photoelectron Spectroscopy. The thermodynamic characteristics of the adsorption process are also studied via statistical mechanics. Finally, determining the influence of the copper cluster size on the adsorption of acrylonitrile allows to extrapolate the properties of the acrylonitrile/Cu͑100͒ surface from those of acrylonitrile/copper clusters.

show abstract

Section: A Geometric Structure Of An Copper Complexesmentioning

confidence: 96%

Section: A Geometric Structure Of An Copper Complexesmentioning

confidence: 99%

Section: A Geometric Structure Of An Copper Complexesmentioning

confidence: 99%

Section: ͑7͒mentioning

confidence: 99%

See 2 more Smart Citations

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

Crispin

Bureau

Geskin

et al. 1999

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…ref. 14 for the system of interest in this work). A widely used technique to study vibrations of molecules adsorbed on surfaces is the (high-resolution) electron energy loss spectroscopy, HREELS.…”

Section: Introductionmentioning

confidence: 99%

Density functional theory study of the structure and vibrational modes of acrylonitrile adsorbed on Cu(100)

Díaz‐Tendero

Alcamı́

Martín

2013

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We present a theoretical study of the structure and vibrations of acrylonitrile adsorbed on a Cu(100) metal surface. Simulations have been carried out by means of the density functional theory adopting periodic boundary conditions and including van der Waals dispersion forces. The two most stable structures (which are almost degenerate in energy) correspond to the molecule adsorbed parallel to the metal surface. In both geometries, the vinyl (C=C) and the cyano (C≡N) groups are the anchorage sites to the surface atoms. Low energy transition barriers allow fast isomerization between both structures. Molecular adsorption shifts some of their vibrational frequencies with respect to the gas phase, mainly the C=C and the C≡N stretching modes, in agreement with recent experimental measurements [Tornero et al., Phys. Chem. Chem. Phys., 2011, 13, 8475].

show abstract

Electrografting of Acrylic and Methacrylic Monomers onto Metals: Influence of the Relative Polarity and Donor–Acceptor Properties of the Monomer and the Solvent

Baute

Teyssié

Martinot

et al. 1998

Eur. J. Inorg. Chem.

View full text Add to dashboard Cite

The possibility of grafting a series of alkyl polyacrylates and polymethacrylates onto a nickel cathode by electropolymerization of the parent monomers has been investigated and has emphasized the critical importance of the solvent used. Indeed, the intensity of the inhibition peak, which is the electrochemical mark of the cathode passivation as result of the polymer grafting, clearly depends on both the polarity and the donor‐acceptor properties of the solvent. The Gutmann concept is used to account for these experimental results. An increase in the donicity of the solvent used for the electrochemical medium has allowed, for the very first time, several polyacrylates and polymethacrylates [such as poly(ethyl acrylate), poly(methyl methacrylate), and poly(2‐trimethylsilyloxyethyl methacrylate)] to be electrografted onto Ni. This observation is consistent with a competition process between the monomer and the solvent for being adsorbed on the cathode and amassing in its very close vicinity. The outcome of this competition is controlled by the relative polarity (in case of low donicity) and the relative donor‐acceptor properties (when the difference is high enough) of the monomer/solvent pair, and by the monomer concentration (in case of weak competition). A semi‐quantitative relationship has also been observed between the monomer ability to be electrografted and the electron‐accepting character of the vinyl β‐carbon atom as measured by 13C NMR.

show abstract

The bonding of acrylonitrile molecules to copper surfaces

Cited by 15 publications

References 40 publications

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

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

Density functional theory study of the structure and vibrational modes of acrylonitrile adsorbed on Cu(100)

Electrografting of Acrylic and Methacrylic Monomers onto Metals: Influence of the Relative Polarity and Donor–Acceptor Properties of the Monomer and the Solvent

Contact Info

Product

Resources

About