t-Butyl nitrite adsorbed on Ag(111): thermally activated structure changes

Lee, Ilkeun; Kim, Seong-Kyu; Zhao, Wei; White, J. M.

doi:10.1016/s0039-6028(01)01815-5

Cited by 4 publications

(7 citation statements)

References 32 publications

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“…TBN TPD has been presented in our previous paper . The monolayer desorbs from Ag(111) at 160 K and the multilayer at 130 K. As noted earlier, the multilayer peak appears before the monolayer saturates.…”

Section: Resultssupporting

confidence: 51%

“…In previous work, we have shown that TPD spectra as a function of TBN coverage show a multilayer contribution before the monolayer is fully saturated. In this paper, we define a standard dose (1 SD) as the highest dose at 80 K for which there is no contribution from the multilayer peak in subsequent TPD.…”

Section: Methodsmentioning

confidence: 86%

“…TBN Surface Structure Model. In previous work, we have shown that TPD spectra as a function of TBN coverage show a multilayer contribution before the monolayer is fully saturated . The results are modeled in terms of relatively strong intermolecular interactions that drive the formation of 3D islands before completion of the first layer.…”

Section: Discussionmentioning

confidence: 93%

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Photodissociation at 193 nm of tert-Butyl Nitrite on Ag(111)

et al. 2004

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The translational and internal state properties of nitric oxide, NO, ejected by 193-nm photodissociation of tert-butyl nitrite, (CH 3 ) 3 CONO, TBN, adsorbed on Ag(111) have been investigated using resonance-enhanced multiphoton ionization time-of-flight (REMPI-TOF) and quadrupole mass spectrometer time-of-flight (QMS-TOF). The results are described in terms of three components depending on the number of collisions along the exit trajectory and are compared to prior work using 248-and 351-nm photons. Although 193-nm photons have higher energy, the characteristic translational energy of the collisionless NO (0.55 eV) lies between that for 248 nm (0.89 eV) and 351 nm (0.39 eV). As for gas-phase photolysis at 193 nm, the NO is rotationally cold (J max ) 15.5), much lower than for both 248-(J max ) 53.5) and 351-nm (J max ) 31.5) photolysis. The NO vibrational distribution is dominated by V′′ ) 1, whereas V′′ ) 0 for 248 nm and V′′ ) 1 and 2 for 351 nm photodissociations, respectively. Angle-resolved REMPI-TOF and QMS-TOF studies give information about the orientation of adsorbed TBN. While TBN is more stable with the C-O-NdO plane perpendicular to surface and the internal O-N bond directed about 40°away from the surface normal, dosing less than a full monolayer at 80 K does not achieve this state fully. Annealing to 110 K is sufficient to realize this molecular orientation. For multilayer coverage dosed at 80 K, the data are consistent with considerable surface roughness compared to a surface annealed at 110 K. IntroductionSurface photochemistry has been of interest for many years. 1-3 Among the motivations are its many potential technological applications, e.g., photochemical lithography, deposition, and etching related to the fabrication of electronic and chemical sensor devices with submicron dimensions. There also continues to be scientific interest in fundamental questions concerning the mechanisms of energy transfer among the radiation field, and the various electronic and nuclear degrees of freedom of adsorbate-substrate systems.The spectroscopy and photodissociation dynamics of aliphatic nitrites (R-O-NdO) have been the subject of much interest. [4][5][6][7][8][9] Typically, gas phase and adsorbed nitrites dissociate upon photolysis and do so through cleavage of the internal O-N bond to from an alkoxide and nitric oxide. Like other nitrites, tertbutyl nitrite (TBN, (CH 3 ) 3 CONO) has three distinct optical absorption bands, the lowest energy band is found between 300 and 400 nm (n f π*, S 1 r S 0 ), and motion on S 1 is characterized as vibrational predissociation. The second band ranges from about 216 to 280 nm (π f π*, S 2 r S 0 ), and motion on S 2 is described as a very fast repulsive dissociation. The third band, rarely studied and related to this paper, ranges from 180 to 216 nm and also leads to dissociation of the internal O-N bond. State-resolved studies of NO reveal very different quantum state distributions depending on the photolysis wavelength. For gas-phase irradiation, photodissociation at 35...

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Section: Resultssupporting

confidence: 51%

Section: Methodsmentioning

confidence: 86%

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Photodissociation at 193 nm of tert-Butyl Nitrite on Ag(111)

et al. 2004

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“…Silver metal is of considerable industrial importance as a catalytic material, for example, in the selective partial oxidation of ethene to its epoxide, which is a widely used precursor for a host of chemical products. , As a consequence of its catalytic significance and also because of the ease with which silver is investigated using surface science techniques such as scanning tunneling microscopy (STM), e.g., refs and , silver surfaces have been the subject of much research, both experimentally, e.g., refs −8, and theoretically, e.g., refs −14. Often, the reactivity of the metal is probed by the adsorption of small molecules, e.g., NO, , CO 2 , or SiO and SiS, while a variety of experimental techniques has been used to study the interactions of silver with a host of small organic adsorbates, such as methanol, phenol, tert -butyl nitrite, and sulfur-containing compounds. − More recently, experimental techniques have been employed to study the synthesis and behavior of silver nanoparticles, e.g., refs and .…”

Section: Introductionmentioning

confidence: 99%

A Computer Modeling Study of Perfect and Defective Silver (111) Surfaces

Leeuw

Nelson

2003

J. Phys. Chem. B

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Density functional theory calculations of the ideal and defective (111) surfaces of silver have shown that although the perfect surface shows very little atomic relaxation the introduction of vacancies, adatoms, and step edges on the surface leads to significant bond distortions in the near-defect regions. The defective surfaces are not significantly less stable than the perfect (111) surface and the average calculated surface energy of 0.49 eV per surface atom agrees well with the experimental value of 0.55 eV/atom. Electron density contour plots show delocalization along the surface compared to the bulk metal, while a more gradual decline of the electron density in the defect areas compared to the perfect surface leads to a more level electronic structure of the defective surfaces than their atomic structure. The formation energies of surface vacancies and adatoms with respect to gaseous silver atoms are +3.20 eV and -2.03 eV, respectively, while the introduction of a step edge on the surface costs 0.42 eV per edge atom with respect to the planar surface. Adsorption of an adatom at the step edge releases 2.50 eV and the lower-coordinated edge sites, rather than the terrace sites of the planar (111) surface, are thus energetically preferred sites for further silver growth. Segregation of vacancies from the bulk material to the (111) surface is calculated to be exothermic at -0.18 eV per vacancy and recombination of a surface vacancy with a surface adatom will release 1.81 eV per vacancy/adatom pair.

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“…30 Similar bands are observed for butyl and propyl nitrite molecules depending upon their conformations. 31,32 There is no characteristic infrared peak in the 1290 cm -1 region for methyl nitrite. In a condensed phase, the equilibrium between NO 2 and N 2 O 4 lies almost completely toward dinitrogen tetraoxide (∼99%).…”

Section: Resultsmentioning

confidence: 99%

Infrared Spectroelectrochemistry of Nitrite in Absolute Methanol

Brooksby

McQuillan

2010

J. Phys. Chem. C

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A highly polished planar Pt electrode was used in an in situ reflection−absorption infrared cell to examine the chemical products of electrochemical reactions of NaNO2 in a methanolic solution in the 2500−1100 cm−1 range. Analysis of the resulting infrared bands showed that methanol reacts directly with the electro-oxidation products of nitrite. The predominant oxidation product was methyl nitrite, with apparent smaller quantities of NO2, NO3 −, and NO. The reduction product of in situ-generated methyl nitrite was N2O, presumed to occur via adsorbed N- and O-type species. No other species arising from N x O y H z were observed; however, bands associated with the stretching modes of O−H and N−H that would clearly identify any such products were outside the accessible spectral range examined here due to interfering absorptions from methanol.

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t-Butyl nitrite adsorbed on Ag(111): thermally activated structure changes

Cited by 4 publications

References 32 publications

Photodissociation at 193 nm of tert-Butyl Nitrite on Ag(111)

Photodissociation at 193 nm of tert-Butyl Nitrite on Ag(111)

A Computer Modeling Study of Perfect and Defective Silver (111) Surfaces

Infrared Spectroelectrochemistry of Nitrite in Absolute Methanol

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