Nature of the interaction of adsorbate molecules with metal ad-atoms

Marinyuk, V. V.; Lazorenko-Manevich, R. M.; Kolotyrkin, Ya.M.

doi:10.1016/s0022-0728(80)80369-x

Cited by 47 publications

(38 citation statements)

References 4 publications

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“…The absence of enhancement of RS spectra for pyridine was registered also on mechanically polished silver in [46] (as opposed to numerous reports about observation of SERS, albeit less intensive, on mechanically polished silver [1,4,5,14,42,47]). Nor was SERS discovered at electrodes subjected to ER and then cathodically polarized for a long time at potentials E ≤ -1.4 V vs. normal hydrogen electrode (NHE) [48] when nonequilibrium silver adatoms, which are SERSactive adsorption centers, which form a complex with pyridine molecules, disappear [42,49] (and this observation is inconsistent with available information about the presence of "residual" SERS after such a cathodic treatment [49,50]).…”

Section: The Magnitude Of Sers Enhancementcontrasting

confidence: 73%

“…Upon covering the surface at levels eluding assay by traditional methods, adatoms are capable of providing for quite measurable values of G . It is precisely this circumstance that could have been the reason for the results reported in [1,4,5,42,47,51]. We stress that enhancement of RS spectrum for pyridine was not discovered at stepwise faces (540) of single-crystal silver [52] when using the surface preparation procedure reported in [44], nor was it discovered on silver faces (521) or (987) containing fractures of steps or "kinks" (see paper by Campion and Mullins in [36]).…”

Section: The Magnitude Of Sers Enhancementmentioning

confidence: 86%

“…The only assumption was that G ≤ 10 2 in the absence of measurable SERS signal (more correctly, a signal discovered against the backdrop of noise), for sensitivity of common RS spectrometers provided for a sure obtaining of unenhanced ("normal") RS signal only from an amount of substance that was equivalent to approximately 100-200 adsorbate monolayers [5,8,42]. It was the level from which RS signal for pyridine after ER of silver increased by three orders of magnitude [2], which was precisely what ensured value G Ӎ 10 5 -10 6 .…”

Section: The Magnitude Of Sers Enhancementmentioning

confidence: 99%

“…Nor was SERS discovered at electrodes subjected to ER and then cathodically polarized for a long time at potentials E ≤ -1.4 V vs. normal hydrogen electrode (NHE) [48] when nonequilibrium silver adatoms, which are SERSactive adsorption centers, which form a complex with pyridine molecules, disappear [42,49] (and this observation is inconsistent with available information about the presence of "residual" SERS after such a cathodic treatment [49,50]). On the other hand, in the case of single-crystal surfaces as well, there were communications that reported on the existence of considerable RS enhancement, specifically, upon pyridine adsorption at the (100) silver face G = 440 [51].…”

Section: The Magnitude Of Sers Enhancementmentioning

confidence: 99%

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Adatom Hypothesis as a Predominant Mechanism of Surface Enhanced Raman Scattering: A Review of Experimental Argumentation

Lazorenko-Manevich¹

2005

Russ J Electrochem

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A contemporary review of research concerning the mechanism of surface enhanced Raman scattering (SERS) is presented and it is stated that this problem is yet to be solved. The necessity to yet once again analyze some of the familiar experimental observations and the deep-rooted beliefs and revise quantitative evaluations of SERS enhancement via major mechanisms (electromagnetic and chemical) with allowance made for most important experimental characteristics of SERS is substantiated. The characteristics are enumerated and the role they play in the above evaluations is sketched. Attention is focused mainly on electrochemical aspects of SERS problem, which to a large extent define the content and salient features of SERS and provide basic experimental justification for the so-called adatom hypothesis.

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Section: The Magnitude Of Sers Enhancementcontrasting

confidence: 73%

Section: The Magnitude Of Sers Enhancementmentioning

confidence: 86%

Section: The Magnitude Of Sers Enhancementmentioning

confidence: 99%

Section: The Magnitude Of Sers Enhancementmentioning

confidence: 99%

See 2 more Smart Citations

Adatom Hypothesis as a Predominant Mechanism of Surface Enhanced Raman Scattering: A Review of Experimental Argumentation

Lazorenko-Manevich¹

2005

Russ J Electrochem

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“…For pyridine adsorbed on silver surfaces, this kind of electronic transition has a transition energy in the range of % 1.4 eV-2.7 eV. [62][63][64] In contrast, the transition energies for pyridine adsorbed on gold surfaces are about 1.55 eV [64] and about 2.4 eV. [65] In a previous paper, the transition energies of CT states were predicted to be 2.05 eV ( 4 .…”

Section: Vibrational Raman Spectra Of Pyàau M Ag Nmentioning

confidence: 93%

Binding Interactions and Raman Spectral Properties of Pyridine Interacting with Bimetallic Silver–Gold Clusters

Ren

Zhang

2006

ChemPhysChem

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The binding interactions between pyridine and bimetallic silver-gold clusters are investigated using density functional theory (DFT). The binding energies of pyridine-bimetallic cluster complexes indicate that the bonding depends strongly on the binding site (Au or Ag atom) and bonding molecular orbitals in a given configuration. The donation of the lone-pair electrons of the nitrogen of pyridine to an appropriate unoccupied orbital of each metal cluster plays an important role. The low-lying excited states and charge-transfer states of four stable complexes of interest are calculated on the basis of a time-dependent DFT method. In nonresonance Raman scattering processes, the influence of binding interactions on the relative Raman intensity of totally symmetric pyridine vibrational modes is discussed. These calculated relative Raman intensities are compared with observed surface-enhanced Raman spectra of pyridine adsorbed on silver-gold alloy surfaces.

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Surface‐enhanced Raman spectra of aromatic amino acids and proteins adsorbed by silver hydrosols

Nabiev

Savchenko

Efremov

1983

J Raman Spectroscopy

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Surface-enhanced Raman spectra of some amino acids (Phe, Tyr, Trp, His, Leu and Ala) and cytotoxin I from Nuja naja uxiana adsorbed by silver hydrosols have been obtained. The spectra are enhanced from 100 to 200 times. Addition of aqueous solutions of the amino acids to the hydrosol resulted in the appearance of an absorption band in the visible spectral range (450-650 nm) due to formation of the hydrosol-amino acid complex. The surface-enhanced Raman spectrum and the absorption band disappear after short ultrasonic treatment of the complex. Comparison of electron microphotographs of the silver hydrosol and the hydrosolprotein complex clearly demonstrate coagulation of the silver micelles, apparently caused by protein adsorption and complex formation. The excitation profile of the Phe-Ag hydrosol complex was obtained and this agreed well with the position of the longwave absorption band. From the analysis of the intensity ratios of the Stokes and anti-Stokes components of the Raman spectra of Phe in the silver hydrosol and in aqueous solution the mechanism of the resonance Raman effect is strongly supported. The problem of possible conformational changes of the adsorbed molecules was considered. From CD spectra of cytotolhn I in aqueous solution and those in the silver hydrosol it was concluded that the backbone conformation of the protein did not change, but the environment of the aromatic residues altered. Experiments on the binding of an equimolar mixture of Phe and Ala with silver hydrosols showed that competitive binding took place, and thus the aromatic amino acid is mainly responsible for the surface-enhanced Raman effect.

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Nature of the interaction of adsorbate molecules with metal ad-atoms

Cited by 47 publications

References 4 publications

Adatom Hypothesis as a Predominant Mechanism of Surface Enhanced Raman Scattering: A Review of Experimental Argumentation

Adatom Hypothesis as a Predominant Mechanism of Surface Enhanced Raman Scattering: A Review of Experimental Argumentation

Binding Interactions and Raman Spectral Properties of Pyridine Interacting with Bimetallic Silver–Gold Clusters

Surface‐enhanced Raman spectra of aromatic amino acids and proteins adsorbed by silver hydrosols

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