The photon-induced reactions of chemisorbed CH3Br on Pt{111}

Radhakrishnan, Ganesan; Stenzel, W.; Hemmen, R.; Conrad, H.; Bradshaw, Alexander M.

doi:10.1063/1.460799

Cited by 31 publications

(12 citation statements)

References 29 publications

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“…They also proposed that CH 3 possessed the C 3v symmetry in accordance with the evidences observed by the experement 11 in HREELS at 255 K as well as our result.…”

Section: Ch 3 /Pt(111)supporting

confidence: 92%

“…Cryer et al 2 first spectroscopically identified the existence of CH 3 under ultrahigh vaccumn (UHV) conditions on Ni(111) with a combination of a molecular beam technique and high-resolution electron energy spectroscopy (HREELS). The CH 3 groups was also identified on Pd(111) 8 using SIMS and XPS, Fe(100) 9 by temperature-programmed reaction spectroscopy (TPRS) and XPS, and Pt(111) 10,11 surfaces by temperature-programmed desorption (TPD), XPS, reflection adsorption infrared spectroscopy (RAIRS), and HREELS techniques.…”

Section: Introductionmentioning

confidence: 99%

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The relationship between adsorption energies of methyl on metals and the metallic electronic properties: A first‐principles DFT study

Wang

et al. 2005

J Comput Chem

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A theoretical study of CH3 adsorbed on the (111) surface of some transition and noble metal surfaces M (M = Cu, Ni, Rh, Pt, Pd, Ag, Au) and on the Fe(100) is presented. We find that the hollow site is preferred more than the top one for Fe, Ni, Rh, and Cu, but it is the other way for Pt, Pd, Au, and Ag. In addition, a good linear relationship was observed between the chemisorption energy and d-band center for Group VIII metals or the square of the coupling matrix element for Group IB metals at the hollow site. Interestingly, with a detailed comparison of the adsorption energies at the top and hollow sites, we find that the adsorption energies among each group are very similar on the top site, which supports the theoretical model of Hammer and Norskov that the coupling between the HOMO of adsorbate and sp states of the metal is dominant and almost equal, and that the second coupling to the d-band contributes less but reflects the change of the adsorption energy. It confirms that the coupling to the d band comprises two opposite factors, that is, the d-band center was attractive and the square of the coupling matrix element was repulsive, such that the contributions from the two factors can counteract each other at the top site.

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“…They also proposed that CH 3 possessed the C 3v symmetry in accordance with the evidences observed by the experement 11 in HREELS at 255 K as well as our result.…”

Section: Ch 3 /Pt(111)supporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

The relationship between adsorption energies of methyl on metals and the metallic electronic properties: A first‐principles DFT study

Wang

et al. 2005

J Comput Chem

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“…CH 3 binds less strongly to the top site of Ni( 111) with E ad of −1.57 eV and becomes metastable on the fcc site of Pt(111) with an approximate E ad of ∼−1.33 eV (we can only find this geometry with a loose convergence criterion). The calculated adsorption energies and harmonic frequencies agree well with previous theoretical predictions, 14,16,18,26 although the predicted frequencies are systematically higher than the experimental ones, 14,22,33 due presumably to the intrinsic error in DFT as well as the harmonic approximation used in the theoretical calculations. Note that Gutieŕrez-Gonzaĺez et al 14 have applied vdW-corrected functionals to study CH 3 adsorbed on Pt surfaces and found similar site preference and site-specific vibrational frequencies as using PBE.…”

supporting

confidence: 83%

“…This is in broad agreement with the PBE results of Nave and Jackson, 26 and the predicted site preference agrees well with the experimental assignments. 23,33 In both cases, the methyl adsorbate forms a pyramidal configuration and bonds with the metal surface with its carbon end. CH 3 binds less strongly to the top site of Ni( 111) with E ad of −1.57 eV and becomes metastable on the fcc site of Pt(111) with an approximate E ad of ∼−1.33 eV (we can only find this geometry with a loose convergence criterion).…”

mentioning

confidence: 99%

Infrared Activities of Adsorbed Species on Metal Surfaces: The Puzzle of Adsorbed Methyl (CH₃)

Zhou

Vejayan

Beck

et al. 2021

J. Phys. Chem. Lett.

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Reflection–absorption infrared spectroscopy (RAIRS) is widely used to identify molecular adsorbates on metals during surface chemical reactions, but the interpretation of RAIRS data can be difficult with experiment alone. Here, we reveal from first-principles calculations the origin of the contrasting RAIRS spectra of methyl adsorbed on Pt(111) and Ni(111). We find that the dynamic dipole associated with the symmetric C–H stretch vibration of CH3 along surface normal is significant on Pt(111) but negligibly small on Ni(111), explaining the strong IR activity in the former and the absence of any RAIRS peaks in the latter. This difference is correlated to different charge transfer patterns between metals and the adsorbate, which are determined by the different preferred adsorption sites of methyl on the two surfaces. This work highlights the need of electronic structure calculations in interpreting RAIRS spectra of adsorbates on metal surfaces.

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“…There is a single detectable absorption band in the C-H stretching region at 2885 cm Ϫ1 and no bands detectable in the low wave number region. In this orientation, the symmetric CH 3 ͑ads͒ deformation that has been observed at ϳ1153 cm Ϫ1 in HREELS measurements, 31 should also be symmetry allowed. Our measured intensity is also consistent with existing literature data on this transition.…”

Section: A Methane and Methylmentioning

confidence: 86%

The chemistry of simple alkyl species on Pt(111) generated by hyperthermal collisions

Oakes¹,

Newell²,

Rutten³

et al. 1996

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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Kinetics and dynamics of the trappingmediated dissociative chemisorption of oxygen on Ru (001) The identification of the primary dissociation products of hyperthermal collisions of methane and ethane with a Pt͑111͒ surface at ϳ150 K and the study of their subsequent thermal evolution has been afforded by the use of reflection-absorption infrared spectroscopy, temperature programmed desorption, and Auger electron spectroscopy. In both cases, the primary dissociation products have been identified as an adsorbed alkyl moiety ͑methyl, CH 3 , and ethyl, C 2 H 5 , respectively͒ and an adsorbed hydrogen atom. The thermal treatment of both alkyl adlayers ultimately results in the formation of the ethylidyne ͑wCCH 3 ͒ moiety at temperatures between 300 and 400 K. At ϳ500 K, this species itself thermally decomposes to yield adsorbed carbon atoms and gaseous hydrogen. While this behavior may not be unexpected for the C 2 ethyl fragment, the formation of the C 2 ethylidyne fragment from the C 1 methyl fragment can only be explained through the occurrence of carbon-carbon coupling reactions. Such reactions have only recently been observed on the Pt͑111͒ surface. The C-C coupling reactions associated with the formation of ethylidyne from methyl show considerable dependence upon the surface coverage of the methyl fragment and are accompanied by the evolution of both gaseous hydrogen and methane. The latter results from recombinative desorption of methyl moieties with adsorbed hydrogen atoms.

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The photon-induced reactions of chemisorbed CH3Br on Pt{111}

Abstract: Articles you may be interested inGiessen coupled-channel model for pion-and photon-induced reactions AIP Conf.

Cited by 31 publications

References 29 publications

The relationship between adsorption energies of methyl on metals and the metallic electronic properties: A first‐principles DFT study

The relationship between adsorption energies of methyl on metals and the metallic electronic properties: A first‐principles DFT study

Infrared Activities of Adsorbed Species on Metal Surfaces: The Puzzle of Adsorbed Methyl (CH₃)

The chemistry of simple alkyl species on Pt(111) generated by hyperthermal collisions

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The photon-induced reactions of chemisorbed CH3Br on Pt{111}

Abstract: Articles you may be interested inGiessen coupled-channel model for pion-and photon-induced reactions AIP Conf.

Cited by 31 publications

References 29 publications

The relationship between adsorption energies of methyl on metals and the metallic electronic properties: A first‐principles DFT study

The relationship between adsorption energies of methyl on metals and the metallic electronic properties: A first‐principles DFT study

Infrared Activities of Adsorbed Species on Metal Surfaces: The Puzzle of Adsorbed Methyl (CH3)

The chemistry of simple alkyl species on Pt(111) generated by hyperthermal collisions

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Product

Resources

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Infrared Activities of Adsorbed Species on Metal Surfaces: The Puzzle of Adsorbed Methyl (CH₃)