Identification of precursor states in the dissociation of adsorbed benzene on Os(0001): A HREELs study

Graen, H.H.; Neumann, M.; Wambach, J.; Freund, H.‐J.

doi:10.1016/0009-2614(90)85418-c

Cited by 13 publications

(10 citation statements)

References 19 publications

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“…The sharp decrease in the relative intensity of the ν 4 modes in the C 6 H 6 and C 6 D 6 spectra on going from on-specular to +20° off-specular detection indicates that the ν 4 mode has a strong dipole scattering component, which suggests (on the basis of the dipole selection rule) that benzene adsorbs with its molecular plane parallel to the plane of the surface. This adsorption geometry is analogous to that found in previous studies of benzene on other single-crystal metal surfaces. − ,,− ,− ,, …”

Section: Results and Interpretationsupporting

confidence: 81%

“…Analogous behavior has been observed previously for ethylidyne formation on the carbide-modified Mo(110) surface . Lastly, we note that studies of benzene decomposition on Os(0001) indicate that the benzyne intermediate that is formed during decomposition adopts an orientation in which the molecular plane is tilted 45° relative to the surface plane …”

Section: Discussionsupporting

confidence: 85%

“…The presence of benzene in many industrially important heterogeneous catalytic reactions has led to numerous studies ,− of benzene adsorption onto single-crystal transition metal surfaces over the past two decades. While these studies have been performed with a wide variety of surface analytical techniques, one of the most informative probes of surface bonding and chemistry has been high-resolution electron energy loss spectroscopy (HREELS), which is the primary analysis technique in the present work.…”

Section: Introductionmentioning

confidence: 99%

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Studies of the Adsorption Geometry and Decomposition Mechanisms of Benzene on Clean and Carbide-Modified Mo(110) Surfaces Using Vibrational Spectroscopy

Eng¹,

Bent²,

Frühberger³

et al. 1997

J. Phys. Chem. B

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The bonding and reactivity of benzene on carbide-modified Mo(110) surfaces have been studied using high-resolution electron energy loss spectroscopy (HREELS) and temperature-programmed desorption (TPD) to investigate the effects of carbide formation on the chemistry of this early transition metal surface. For comparison, the reactions of benzene with both clean Mo(110) and oxygen-modified Mo(110) surfaces have been studied as well. We find that benzene adsorbs on all three types of surfaces at 80 K with the molecular plane parallel to the surface. For the case of benzene adsorption on the oxygen-modified surface, the similarity between the vibrational frequencies observed in the HREELS spectrum and infrared spectrum of liquid benzene indicates that benzene interacts only weakly with this surface. On the clean Mo(110) surface, the HREELS data show that adsorption occurs on only one type of surface site, and the benzene layer is stable to at least 325 K. Between 325 and 350 K, benzene decomposes to form benzyne, as proposed earlier by Liu et al. Finally, for the carbide-modified surface, it is observed that the benzene decomposes above ∼350 K to produce C x H y fragments. The latter reactivity is similar to what is observed for benzene on the platinum group metals, especially on Rh(111).

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Section: Results and Interpretationsupporting

confidence: 81%

Section: Discussionsupporting

confidence: 85%

Section: Introductionmentioning

confidence: 99%

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Studies of the Adsorption Geometry and Decomposition Mechanisms of Benzene on Clean and Carbide-Modified Mo(110) Surfaces Using Vibrational Spectroscopy

Eng¹,

Bent²,

Frühberger³

et al. 1997

J. Phys. Chem. B

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“…On the other hand, it is reported that benzene ordered structures may be obtained by the influence of small amounts of coadsorbates such as CO. 11 Although the adsorption of benzene has been studied intensively, there are only a few structural studies of benzene fragments such as benzyne (C 6 H 4 ). Benzyne has been identified as a possible stable precursor of complete benzene decomposition on Mo͕110͖, 12,13 Os͕0001͖, 14,15 and Ni͕110͖. 16 The benzyne is reported to be tilted around 45°on Os͕0001͖ by angle-resolved ultraviolet photoelectron spectroscopy ͑ARUPS͒.…”

Section: Introductionmentioning

confidence: 99%

“…16 The benzyne is reported to be tilted around 45°on Os͕0001͖ by angle-resolved ultraviolet photoelectron spectroscopy ͑ARUPS͒. 14,15 Adsorption and thermal decomposition of iodobenzene on Pt͕111͖ is thought also to form phenyl (C 6 H 5 ) and benzyne intermediates, which are tilted at roughly 73°, according to high-resolution electron energy loss spectroscopy ͑HREELS͒. 17 A recent variable-temperature scanning tunneling microscopy ͑STM͒ study on Cu͕001͖ 18 showed the dissociation of benzene to benzyne was induced by the STM tip and the resulting fragment was adsorbed perpendicular to the surface.…”

Section: Introductionmentioning

confidence: 99%

Origin and consequences of aromatic back-bonding at a transition metal surface: Benzyne on Ir{100}

Yamagishi

Jenkins

King

2002

The Journal of Chemical Physics

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Articles you may be interested inA DFT study of the NO dissociation on gold surfaces doped with transition metals J. Chem. Phys. 138, 074701 (2013); 10.1063/1.4790602 Trends in C-O and C-N bond formations over transition metal surfaces: An insight into kinetic sensitivity in catalytic reactionsRecent low energy electron diffraction experiments have shown that partial dissociation of benzene at the Ir͕100͖ surface yields an ordered overlayer of ortho-benzyne radicals (C 6 H 4 ) with ring-planes inclined at 47.2°to the normal. The primary molecule-surface interaction may be attributed to bonds between radical C and surface Ir atoms, but this characteristic alone does not uniquely constrain the adsorbate to the observed orientation. Through first-principles density functional theory which gives good agreement with the experimental structure, we now demonstrate that the molecular tilt arises due to interaction of the aromatic orbitals with the surface d orbitals, and not because of any dispersive intermolecular forces.

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2018

Vibrational Spectra of Organometallics

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Identification of precursor states in the dissociation of adsorbed benzene on Os(0001): A HREELs study

Cited by 13 publications

References 19 publications

Studies of the Adsorption Geometry and Decomposition Mechanisms of Benzene on Clean and Carbide-Modified Mo(110) Surfaces Using Vibrational Spectroscopy

Studies of the Adsorption Geometry and Decomposition Mechanisms of Benzene on Clean and Carbide-Modified Mo(110) Surfaces Using Vibrational Spectroscopy

Origin and consequences of aromatic back-bonding at a transition metal surface: Benzyne on Ir{100}

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