The geometric structure of the surface methoxy species on Cu(111)

Hofmann, Philip; Schindler, K.‐M.; Bao, Sheng; Fritzsche, V.; Ricken, D. E.; Bradshaw, A. M.; Woodruff, D.P.

doi:10.1016/0039-6028(94)90754-4

Cited by 90 publications

(41 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Moreover, the theoretical studies 4,9,10 overestimated the oxygen-surface distance (0.147 and 0.145 nm respectively), which was significantly longer than the value (0.131±0.006 nm) obtained by Johnston et al 6 and other experimental studies. 7,8 In comparison, the values obtained in this paper (0.1270-0.1300 nm) are in good agreement with the experimental results. In one word, the predicted results obtained in this paper are reasonable and reliable.…”

Section: Methoxy Adsorption On Cu(111) Surfacesupporting

confidence: 93%

“…6,8 The methoxy species is adsorbed with its C-O axis almost normal to the surface, with an upright geometry of pseudo-C 3v local symmetry as seen in Figure 3, which is consistent with the work by Gomes and coworkers. 4,10 It is now worthwhile to compare our results with previous theoretical and experimental work.…”

Section: Methoxy Adsorption On Cu(111) Surfacesupporting

confidence: 85%

“…Surface EXAFS, NEXAFS 7 and energy scanned photoelectron diffraction (PED) 8 have been used to determine the structure of the methoxy moiety on Cu(111) surface. In the SEXAFS and NEXAFS studies it was found that the methoxy species occupied a threefold hollow site and the C-O bond was nearly perpendicular to the surface.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Adsorption of Methanol and Methoxy on Cu(111) Surface: A First‐principles Periodic Density Functional Theory Study

et al. 2006

View full text Add to dashboard Cite

Adsorption of methanol and methoxy at four selected sites (top, bridge, hcp, fcc) on Cu(111) surface has been investigated by density functional theory method at the generalized gradient approximation (GGA) level. The calculation on adsorption energies, geometry and electronic structures, Mulliken charges, and vibrational frequencies of CH 3 OH and CH 3 O on clean Cu(111) surface was performed with full-geometry optimization, and compared with the experimental data. The obtained results are in agreement with available experimental data. The most favorite adsorption site for methanol on Cu(111) surface is the top site, where C-O axis is tilted to the surface. Moreover, the preferred adsorption site for methoxy on Cu(111) surface is the fcc site, and it adsorbs in an upright geometry with pseudo-C 3v local symmetry. Possible decomposition pathways also have been investigated by transition-state searching methods. Methoxy radical, CH 3 O, was found to be the decomposition intermediate. Methanol can be adsorbed on the surface with its oxygen atom directly on a Cu atom, and weakly chemisorbed on Cu(111) surface. In contrast to methanol, methoxy is strongly chemisorbed to the surface.

show abstract

Section: Methoxy Adsorption On Cu(111) Surfacesupporting

confidence: 93%

Section: Methoxy Adsorption On Cu(111) Surfacesupporting

confidence: 85%

See 1 more Smart Citation

Adsorption of Methanol and Methoxy on Cu(111) Surface: A First‐principles Periodic Density Functional Theory Study

et al. 2006

View full text Add to dashboard Cite

show abstract

“…[27][28][29] Methoxy is found to be formed either directly or through reaction with oxygen on most surfaces and is found to display a C 3v symmetry for most coverages on Cu͑100͒, 14,18 Cu͑111͒, 15,19,29,30 Ni͑100͒, 16 Ni͑111͒, 20 Mo͑110͒, 17 and Ag͑111͒. 6 This means that the C-O axis is oriented normal to the surface and that the ␦ as ͑CH 3 ͒ modes are degenerate.…”

Section: Introductionmentioning

confidence: 94%

Fermi resonance coupling in a surface adsorbate: The C–H stretch in methoxy adsorbed on Cu(100) calculations and experiments

Ásmundsson

Uvdal

2000

The Journal of Chemical Physics

View full text Add to dashboard Cite

The C–H stretch spectrum of methoxy adsorbed on Cu(100) has been measured using Fourier transform infrared spectroscopy. Fermi resonance coupling constants in methoxy are calculated using a normal mode model where the unperturbed modes were either experimentally determined or inferred from ab initio calculations performed for a methoxy-Mo model complex. The measured frequency shifts and intensity redistribution observed in the C–H stretch region are qualitatively reproduced by the calculations.

show abstract

“…14 Methoxy is found to be located in the threefold hollow site with the -C atom positioned 2.8 Å above the surface atom plane. 19 It is likely, however, that ethoxide is even further from the surface as a result of the steric effects of the larger methyl group. Another unknown in the model is the position of the image plane with respect to the real metal surface.…”

Section: Resultsmentioning

confidence: 99%

Inductive Substituent Effects: Metal Surfaces versus the Gas Phase

Buelow¹,

Gellman²

2000

J. Phys. Chem. B

View full text Add to dashboard Cite

The influence of metal surfaces on inductive (or electrostatic field) substituent effect measurements for surface reactions has been evaluated using image charge theory. Substituent effects have been a valuable tool for determining the electronic properties of transition states for reactions in many environments but have not received much use or consideration on metal surfaces. An important mechanism by which substituents can alter the activation barrier of a reaction is through local dipole field effects on a charged reaction center. To evaluate the influence of a nearby metal surface, substituent field effects have been modeled by considering a point charge and a dipole, both positioned above a conductive surface, that interact electrostatically with their corresponding images at equal distances below the surface. It has been found that the magnitude of substituent effects for reactions on metal surfaces will be approximately equal to the gas-phase value for geometries in which the substituent is farther from the surface than the reaction center and both are above the image plane. This model was used to describe -hydride elimination from ethoxides on Cu(111). This reaction has been found to have a substituent effect that correlates with the reaction energetics of gas-phase alcohol dehydrogenation, a result that is in agreement with the image charge model of the electrostatic influence of the metal.

show abstract

The geometric structure of the surface methoxy species on Cu(111)

Cited by 90 publications

References 35 publications

Adsorption of Methanol and Methoxy on Cu(111) Surface: A First‐principles Periodic Density Functional Theory Study

Adsorption of Methanol and Methoxy on Cu(111) Surface: A First‐principles Periodic Density Functional Theory Study

Fermi resonance coupling in a surface adsorbate: The C–H stretch in methoxy adsorbed on Cu(100) calculations and experiments

Inductive Substituent Effects: Metal Surfaces versus the Gas Phase

Contact Info

Product

Resources

About