The effect of attractive lateral interactions on flash-desorption spectra

Golze, Manfred; Grunze, M.; Hirschwald, W.

doi:10.1016/0042-207x(81)90098-1

Cited by 44 publications

(8 citation statements)

References 7 publications

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“…Niemantsverdriet and Wandelt simulated TPD spectra taking into account the compensation effect and showed that a shift in TPD peak maxima at various coverages does not necessarily reflect the expected attractive or repulsive nature of the interactions, , as one might conclude based on a Redhead analysis. Although it is generally concluded that a shift in the maximum of the TPD spectra to higher temperatures indicates attractive lateral interactions and a shift to lower temperatures indicates repulsive lateral interactions, Niemantsverdriet points out that these conclusions hold true only if the preexponential factor is constant and independent of coverage. But when the preexponential factor is not constant and is coverage dependent, the peaks may in fact shift to lower temperatures even when attractive interactions are present, or to higher temperatures even when repulsive interactions are present, especially when the interaction energy is significant.…”

Section: Resultsmentioning

confidence: 99%

Interfacial Interactions between a Carboxyl-Terminated Monolayer and Various n-Alcohols

Vogt

Beebe

1999

Langmuir

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The interactions of vapor-deposited methanol, ethanol, 1-propanol, and 1-hexanol with an 11-mercaptoundecanoic acid (HOOC(CH2)10SH) self-assembled monolayer adsorbed on a nickel(111) single crystal were studied in ultrahigh vacuum by temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). The peak shapes of the TPD spectra for methanol, ethanol, and propanol desorption are similar, suggesting that these alcohols undergo similar desorption processes. Their peak desorption temperatures at the lowest submonolayer fluences increased with the number of carbons in the alcohol, suggesting that the methyl and methylene groups, as well as the hydroxyl group, participate in the adsorbed alcohol monolayer's interactions at the acid-terminated self-assembled monolayer surface. Threshold TPD (TTPD) was used for a quantitative analysis of the desorption spectra as a function of coverage. The structure and behavior of hexanol's desorption spectra suggest a different desorption process than its lower-molecular-weight analogues. Of all the alcohols studied, hexanol exhibited the strongest interaction with the acid-terminated surface. The desorption energies calculated by the TTPD method for the straight-chain n-alcohols C1−C3 (15−20 kJ mol-1) and C6 (∼38 kJ mol-1) in the submonolayer regime were in the range expected (10−40 kJ mol-1) for hydrogen bonding.

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Section: Resultsmentioning

confidence: 99%

Interfacial Interactions between a Carboxyl-Terminated Monolayer and Various n-Alcohols

Vogt

Beebe

1999

Langmuir

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“…The main problem is that for the majority of systems no quantitative experimental data are available. In principle, values for interaction energies can be extracted from measurements of the coverage dependence of adsorption energies which may be obtained by temperature programmed desorption ͑TPD͒, 8 measurements of isotherms, 9 or microcalorimetry. 10 However, these methods do not provide the distance dependence of the interactions, and a quantitative analysis of the TPD data, which are mostly the only ones available, is not unequivocal.…”

Section: Introductionmentioning

confidence: 99%

Adsorbate-adsorbate interactions from statistical analysis of STM images: N/Ru(0001)

et al. 1996

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Atomic nitrogen on Ru͑0001͒ was prepared by dissociative chemisorption of N 2 and studied by scanning tunneling microscopy ͑STM͒ at 300 K. Nitrogen occupies the hcp threefold hollow site and is imaged as a depression with a diameter of about 5 Å. Interactions between the adsorbed nitrogen atoms were obtained by statistical analysis of STM images, by extraction of the two-dimensional pair distribution function from the arrangement of the N atoms. Since the nearest-neighbor separations could be identified with atomic precision, the pair distribution function g and hence the potential of mean force V eff were obtained as a function of the discrete neighbor sites j up to the tenth nearest neighbor. A comparison with Monte Carlo calculations for balls with a hard-sphere potential provides information about the pair potential V pair ( j): The nearest-neighbor site is strongly repulsive, the second-neighbor site is weakly repulsive, and the third-neighbor site is weakly attractive. These findings rationalize the absence of island formation and of a well-ordered 2ϫ2 phase for the N/Ru͑0001͒ system: At temperatures у300 K the attractive interaction on the third-neighbor site is too weak, while at lower temperatures the diffusion barrier of 0.9 eV represents a kinetic obstacle. The fact that the range of the interaction is identical to the diameter of the N-atom features in the STM topographs is taken as evidence that the interaction is caused by substrate-mediated electronic forces.

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“…with E 0 = E(O = 0), w the interaction energy (negative for attractive and positive for repulsive interactions), and 0 the adsorbate coverage in monolayers (ML) [1][2][3][4][5]. Calculated desorption traces based on pairwise lateral interactions between the adsorbed particles by Golze et al [5] show that in the case of first-order desorption kinetics, attractive interactions shift the desorption peaks to higher temperatures, whereas repulsive interactions shift the peaks to lower temperatures.…”

Section: Introductionmentioning

confidence: 99%

“…Calculated desorption traces based on pairwise lateral interactions between the adsorbed particles by Golze et al [5] show that in the case of first-order desorption kinetics, attractive interactions shift the desorption peaks to higher temperatures, whereas repulsive interactions shift the peaks to lower temperatures. These calculations, however, rest on the assump-0169-4332/88/$03.50 © Elsevier Science Publishers B.V.…”

Section: Introductionmentioning

confidence: 99%

“…Thermal desorption spectroscopy (TDS) constitutes an important tool in order to study interactions between adsorbates and substrates as well as lateral interactions between adsorbates on surfaces [1][2][3][4][5]. On an otherwise homogeneous substrate the presence of lateral interactions can be inferred form the coverage dependence of the activation energy of desorption, E(O).…”

Section: Introductionmentioning

confidence: 99%

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The compensation effect and the manifestation of lateral interactions in thermal desorption spectroscopy

Niemantsverdriet

Markert

Wandelt

1988

Applied Surface Science

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The effect of attractive lateral interactions on flash-desorption spectra

Cited by 44 publications

References 7 publications

Interfacial Interactions between a Carboxyl-Terminated Monolayer and Various n-Alcohols

Interfacial Interactions between a Carboxyl-Terminated Monolayer and Various n-Alcohols

Adsorbate-adsorbate interactions from statistical analysis of STM images: N/Ru(0001)

The compensation effect and the manifestation of lateral interactions in thermal desorption spectroscopy

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