Aniline on Ag(111): Adsorption configuration, adsorbate–substrate bond, and inter-adsorbate interactions

Rockey, Thomas J.; Yang, Minchul; Dai, Hai‐Lung

doi:10.1016/j.susc.2005.05.048

Cited by 19 publications

(23 citation statements)

References 37 publications

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“…This estimate therefore suggests that each ring in the pentacene molecule donates a charge of roughly 0.13 e to the silver surface. This charge transfer value is in agreement with our prior studies of naphthalene, 46 tetracene, 32 benzene, 43 and aniline, 45 in which each phenyl ring of the adsorbate was found to contribute roughly 0.1 e (naphthalene and tetracene) to 0.2 e (aniline and benzene) to the Ag(111) surface. Similar to the sub-monolayer spectra (Fig.…”

Section: B Charge-transfer Bonding Between Pentacene and Ag(111)supporting

confidence: 92%

“…The apparent overestimate of the deduced change in the work function is fully consistent with prior studies of aromatic molecules adsorbed on metal surfaces. 32,43,45,46 Changes in the substrate work function deduced from interface dipole moments tend to be roughly two times larger compared to values deduced from photoelectron spectroscopy results (e.g., -1.2 vs. -0.7 eV for benzene, -1.5 vs. -0.7 eV for tetracene). 19,43,46,49 Overestimation of the dipolededuced ∆Φ values has previously been attributed to contributions from additional repulsive interactions (e.g., inter-adsorbate repulsion), rather than simply the dipoledipole repulsion, which results in an overestimation of the actual interface dipole moment.…”

Section: B Charge-transfer Bonding Between Pentacene and Ag(111)mentioning

confidence: 64%

“…40 Each alkali atom is assigned a single point dipole. This model has since been successfully applied to smaller aromatic molecules (i.e., containing only one or two aromatic rings, such as benzene, 43 aniline, 44,45 and naphthalene 46 ) on Ag(111), but its application to larger aromatic molecules like pentacene may not be appropriate. The primary concern here is the delocalization of charge over the length of the molecule, which makes the single point dipole assumption employed in the Albano formulation insufficient.…”

Section: The α 2 Phase: Diffuse Terrace Adsorptionmentioning

confidence: 99%

“…15% reduction in the deduced interface dipoles for each of these adsorbates. 45 Consequently, given that the uncertainty in the fit-deduced dipole moment for the α 3 phase of pentacene is over 25%, no adjustments to the uncertainty of µ α3 will be made.…”

Section: Modeling Sub-monolayer Pentacene Desorption From Ag(111)mentioning

confidence: 99%

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Ultrathin Films of Pentacene on Ag(111): Charge-Transfer Bonding and Inter-Adsorbate Interactions

Rockey

Wilhelm

Dai

2020

Preprint

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Temperature programmed desorption (TPD) was used to examine the surface binding and intermolecular interactions of mono- and multi-layer thin films of the polycyclic aromatic acene, pentacene, deposited on a Ag(111) surface. The TPD spectra of sub-monolayer cov- erages revealed the presence of three distinct phases (denoted as α1, α2, and α3). The α1 phase was attributed to adsorption on step sites, while the α2 and α3 phases were assigned to adsorption on terrace sites under different local molecular densities. A physical model was constructed to describe the desorption kinetics from each of the three monolayer phases, including intermolecular repulsion from interfacial dipoles produced as a result of charge transfer bonding between pentacene and the Ag substrate. Fit analysis of the sub-monolayer spectra revealed desorption energies in the zero-coverage limit of 218±8, 166±8, and 162±9 kJ/mol for the α1, α2, and α3 phases, respectively. The interface dipoles of the α2 and α3 terrace adsorption sites were found to be effectively invariant (within error) and deduced as 18±7 and 23±10 D, respectively. These values suggest a partial charge transfer of 0.6 to 0.7 electrons from each pentacene molecule to the Ag substrate and is equivalent to 0.13 electrons per aromatic ring. The TPD spectra from the multilayer films also exhibited three phases. Leading edge analysis of the lowest temperature multilayer peak yielded a desorption energy of 121±15 kJ/mole, while simulations predicted desorption energies ca. 10-15 kJ/mole higher for the higher temperature phases. The three multilayer phases were assigned, from lowest to highest temperature, as an amorphous bulk film, a thin film, and polycrystalline structures.

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Section: B Charge-transfer Bonding Between Pentacene and Ag(111)supporting

confidence: 92%

Section: B Charge-transfer Bonding Between Pentacene and Ag(111)mentioning

confidence: 64%

Section: The α 2 Phase: Diffuse Terrace Adsorptionmentioning

confidence: 99%

Section: Modeling Sub-monolayer Pentacene Desorption From Ag(111)mentioning

confidence: 99%

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Ultrathin Films of Pentacene on Ag(111): Charge-Transfer Bonding and Inter-Adsorbate Interactions

Rockey

Wilhelm

Dai

2020

Preprint

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“…Weaver et al studied the aniline electroxidation process at gold–aqueous interfaces by SERS 31. The Raman spectra of aniline have also been observed by Shindo et al 32, 33 They studied the SERS spectra of aniline adsorbed on an Ag electrode, and found that aniline was adsorbed ‘face‐on’ on the electrode at − 1.0 V. Dai et al 34 found that the adsorption of a submonolayer aniline on the Ag(111) surface was nearly flat with a small tilt angle (−13 ± 8° between the CN bond and the surface) and a small orientation angle. Chis and coworkers27 studied the normal Raman and SERS spectra of p ‐nitro aniline (pNA, one of aniline‐based compounds) in the solid state and in ethanol solution through experiments and DFT calculation methods.…”

Section: Introductionmentioning

confidence: 91%

Adsorption of aniline on silver mirror studied by surface‐enhanced Raman scattering spectroscopy and density functional theory calculations

Xie

et al. 2011

J Raman Spectroscopy

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The adsorption of aniline on a silver mirror was studied by surface-enhanced Raman scattering (SERS) spectroscopy and density functional theory (DFT) calculation methods. The normal Raman and SERS spectra of pure aniline liquid and its solutions were recorded by a micro-Raman spectrometer with excitation at 514.5 nm. Orientation of the aniline molecule adsorbed on the Ag mirror is discussed. The results indicate that pure aniline is adsorbed on the surface of the Ag mirror with a tilted orientation. The conformer with the nitrogen atom interacting with the metal surface would be dominant. DFT calculations further confirm the experimental results that charge transfer (CT) takes place from the highest occupied molecular orbital(HOMO) of aniline to the singly occupied molecular orbital (SOMO) of the silver surface. In this paper, the frontier molecular orbital theory has been successfully used to explore the interaction between the aniline molecule and the silver surface.

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High Resolution Electron Energy‐Loss Spectroscopy

Soriaga

Chen

Ding

et al. 2005

Encyclopedia of Inorganic Chemistry

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The determination of the identity and structure of molecular species present in no more than monolayer quantities at solid surfaces is one of the more difficult tasks in interfacial science. In this regard, vibrational spectroscopy is an invaluable technique; in the evaluation of the molecular integrity of surface‐bound compounds, it has few equals. Optical methods such as infrared spectroscopy, while rather uncomplicated for bulk materials, lack the high sensitivity needed for most surface species due to minuscule molecular amounts. A much more responsive alternative is based on the use of low‐energy electrons to interact with the molecular oscillators on the surface. If inelastic interactions occur, the energy of the backscattered electrons will be lower than that of the incident electrons, and the energy loss will correspond to a vibrational‐mode frequency. The present article briefly describes the fundamental principles of and instrumental considerations in high‐resolution electron energy‐loss spectroscopy (HREELS), and cites seminal applications in the study of the adsorption of organic and inorganic molecules at metal and semiconductor surfaces. A limited list of HREELS work published since the turn of the century is added in the last section.

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Aniline on Ag(111): Adsorption configuration, adsorbate–substrate bond, and inter-adsorbate interactions

Cited by 19 publications

References 37 publications

Ultrathin Films of Pentacene on Ag(111): Charge-Transfer Bonding and Inter-Adsorbate Interactions

Ultrathin Films of Pentacene on Ag(111): Charge-Transfer Bonding and Inter-Adsorbate Interactions

Adsorption of aniline on silver mirror studied by surface‐enhanced Raman scattering spectroscopy and density functional theory calculations

High Resolution Electron Energy‐Loss Spectroscopy

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