Enhanced Raman effect from cyanide adsorbed on a silver electrode

Billmann, J.; Kovacs, G. J.; Otto, A.

doi:10.1016/0039-6028(80)90250-2

Cited by 244 publications

(60 citation statements)

References 47 publications

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“…Physical reasons for this fact are still an open problem (see, e.g., [18][19][20][21] for relevant reviews). In the literature several explanations have been put forward for this phenomenon, such as: (i) adatomsubstrate interactions [22][23][24], (ii) charge-carrier excitations [25], (iii) surface electronic states due to chemisorption bonds [26] or (iv) adsorbed carbon impurities [27][28][29][30][31][32]. A combination of causes (i), (iii) and (iv) has also been considered [33].…”

Section: Sers Backgroundmentioning

confidence: 97%

Electrodeposition of Cu from Acidic Sulphate Solutions in the Presence of PEG - Part II Visible Electroreflectance Spectroscopy Measurements during Electrodeposition

2005

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This paper reports in situ visible electroreflectance measurements carried out during potentiostatic electrodeposition of Cu from acidic sulphate solutions in the absence and presence of PEG. Time-dependent electroreflectance spectroscopy gives information on the evolution of the electronic structure of the growing film, yielding new insight into the electrocrystallisation mode. Roughness effects and purely optical quantities were separated by operating in a suitable range of visible wavelengths. Optical transients were followed with a simple model correlating the relative spectral reflectivity and the degree of dispersion of Cu crystallites. Electroreflectance data were complemented by Raman surface-enhancement measurements and scanning electron microscopy. Electroreflectance results can be correlated with the surface morphology and with the formation of Cu clusters giving rise to different degrees of Raman surface enhancement.

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Section: Sers Backgroundmentioning

confidence: 97%

Electrodeposition of Cu from Acidic Sulphate Solutions in the Presence of PEG - Part II Visible Electroreflectance Spectroscopy Measurements during Electrodeposition

2005

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“…King and co-workers suggested that SERS results from the image field arising from the metal surface. 2 2 9 In these models, the enhancement is a result of extraordinarily large local fields in the vicinity of metallic spheres of small diameter. A roughened surface is then imagined to be a collection of such spheres.…”

Section: Introductionmentioning

confidence: 99%

Site symmetry of surface adsorbed molecules

Nichols

Hexter

1981

The Journal of Chemical Physics

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A procedure for determining the allowed local site symmetry groups S for surface adsorbed molecules is presented. An analogy can be drawn between the perturbing field experienced by a matrix isolated molecule in a three-dimensional crystal and that experienced by a molecule adsorbed on a surface. In the former case the field has the symmetry of the host lattice site whereas in the latter case the field has the symmetry of the adsite. If the surface is viewed as a homogeneous two-dimensional plane, then the symmetry of the adsite is described by the group G = C∞v. If the surface cannot be viewed as an unstructured homogeneous plane so that the perturbing field experienced by the adsorbed molecule must be considered on a microscopic level, then the adsite symmetry will be described by the group appropriate for the substrate atoms. This can only be one of the groups G = Cn or G = Cnv. The symmetry operations of the local site symmetry group S consist of an operation in the molecular point group M applied to the molecule combined with an operation in G applied to the substrate. A mapping of the operations in M and G to operations in their isomorphous Longuet-Higgins groups allows the operations to be identified as permutation P or permutation–inversion P operations. The operations in S are restricted to be combinations of P operations in M with P operations in G and P operations in M with P operations in G. An adsorbed molecule having M = D3h symmetry is used as an example to demonstrate the procedure for determining S. The local site symmetry group of the adsorbed molecule is, in general, different for the homogeneous surface approximation as opposed to the microscopic surface approximation. An attempt is made to apply predicted spectroscopic selection rules to adsorbed pyridine and ethylene. Several factors which complicate the interpretation of Raman spectra of molecules adsorbed on metal surfaces are discussed, one of these being depolarization effects due to rough surfaces.

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“…This background was observed in SERS spectra for the metal interface with both vacuum [163,278,279] and solution [43,55,62,[233][234][235][280][281][282][283] (see also paper by Timper et al in [28]), no matter with or without scattering adsorbate molecules. The background intensity depends on the surface treatment.…”

Section: "Gigantic" Background In Sers Spectramentioning

confidence: 97%

“…The very first determinations [1-3, 5, 42], which were then confirmed again and again by different authors, showed that under some conditions G can reach values of 10 5 − 10 6 for the case of pyridine on a silver electrode subjected to operation of electrochemical roughening (ER) provided by the so called oxidation-reduction cycle (ORC). Values of G Ӎ 10 7 were found in the case of adsorption of ion CN -on silver [43]. The electrochemical roughening, which a prerequisite for observing SERS, consists of single-time or cyclic electrooxidation of silver (as well as copper or gold) in a working or a specially prepared solution and a subsequent electroreduction of the oxidation product [4].…”

Section: The Magnitude Of Sers Enhancementmentioning

confidence: 99%

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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Enhanced Raman effect from cyanide adsorbed on a silver electrode

Cited by 244 publications

References 47 publications

Electrodeposition of Cu from Acidic Sulphate Solutions in the Presence of PEG - Part II Visible Electroreflectance Spectroscopy Measurements during Electrodeposition

Electrodeposition of Cu from Acidic Sulphate Solutions in the Presence of PEG - Part II Visible Electroreflectance Spectroscopy Measurements during Electrodeposition

Site symmetry of surface adsorbed molecules

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

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