Surface enhanced Raman scattering and local photoemission currents on the freshly prepared surface of a silver electrode

Funtikov, A.M.; Sigalaev, S. K.; Kazarinov, V.E.

doi:10.1016/0022-0728(87)80107-9

Cited by 42 publications

(30 citation statements)

References 24 publications

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“…6. At Ag electrodes, SERS of water has been observed at potentials below 1.0 V SCE with laser radiation of 514.5, 22 Fig. 6, where the relative band intensity and HER current are displayed).…”

Section: Previous Resultsmentioning

confidence: 99%

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Electronic effects in SERS by liquid water

Chen

Otto

2005

J Raman Spectroscopy

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By exploiting the attenuated total reflection (ATR)-Otto configuration, surface-enhanced Raman scattering of water at monocrystalline copper and silver electrodes in 0.1 M Na 2 SO 4 was observed at cathodic electrode potentials with hydrogen evolution at a laser wavelength of 647.1 nm. The proposed enhancement model is based on the condition that the upshift of the Fermi level of the electrode and the absorption of one laser photon allow an electron of the electrode at the Fermi level to reach the lower level of the energy band of delocalized electrons in liquid water. The electron interaction with the water molecules in the first hydration shell of cations in the Helmholtz plane is so-called impulse scattering, which is the short-time, non-resonant excursion to the anionic ground state of molecules known for a long time in low-energy electron scattering from free molecules.

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Section: Previous Resultsmentioning

confidence: 99%

“…Triggered by a publication by Funtikov et al, 22 the group of Tian started systematic work described in detail in Refs. 21 and 23 to understand the cause of SERS of water under the condition of hydrogen evolution.…”

Section: Introductionmentioning

confidence: 99%

Electronic effects in SERS by liquid water

Chen

Otto

2005

J Raman Spectroscopy

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“…An interesting version of ER creating a SERS-active surface with very intriguing properties was described in [84][85][86]. The ER was conducted in 0.2 M Na 2 SO 4 by anodically dissolving up to a few tens of silver monolayers (~10 µC cm -2 ) with subsequent fast (within 10 -4 -10 -5 s) switching-over of potential to E ≤ -1.3 V vs. silver-silver chloride reference electrode (Ag/AgCl) in a saturated KCl solution.…”

Section: Effect Of Surface Structure On the Magnitude Of Sers Enhancementioning

confidence: 99%

“…The surface, obtained as a result of back electrodeposition of silver in this boosted regime, was SERS-active only at potentials more negative than the potential of zero charge E zc of silver and lost its SERS activity irreversibly upon going into region of stability of common SERS-active surfaces produced by slowly passing from anodic cycle of ER to cathodic. The authors of [84][85][86] believe that severely nonequilibrium SERS-active structures form on such a surface, excited in which are localized surface plasmons, which are responsible for the existence of exceedingly strong local electromagnetic fields in solution near the surface. According to [84][85][86], the presence of fields that strong is confirmed by the fact of intensive photoemission of electrons with the occurrence of a second-order reaction by hydrated electrons with water at illumination intensities common for photoemission experiments.…”

Section: Effect Of Surface Structure On the Magnitude Of Sers Enhancementioning

confidence: 99%

“…The authors of [84][85][86] believe that severely nonequilibrium SERS-active structures form on such a surface, excited in which are localized surface plasmons, which are responsible for the existence of exceedingly strong local electromagnetic fields in solution near the surface. According to [84][85][86], the presence of fields that strong is confirmed by the fact of intensive photoemission of electrons with the occurrence of a second-order reaction by hydrated electrons with water at illumination intensities common for photoemission experiments. In the absence of acceptors of hydrated electrons, this reaction is possible only in the vicinity of assumed SERS-active structures at local concentrations of hydrated electrons that exceed values averaged over the surface by at least two orders of magnitude.…”

Section: Effect Of Surface Structure On the Magnitude Of Sers Enhancementioning

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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