POTENTIAL DEPENDENCE OF SERS SCATTERING (PIPERIDINE).
Item
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Title
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POTENTIAL DEPENDENCE OF SERS SCATTERING (PIPERIDINE).
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Identifier
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AAI8401486
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identifier
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8401486
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Creator
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SANCHEZ, LUIS ANTONIO.
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Contributor
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John R. Lombardi | Ronald L. Birke
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Date
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1983
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Physical
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Abstract
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The effect of the supporting electrolyte and the applied potential on the SERS spectrum of piperidine adsorbed at a polycrystalline Ag electrode was studied. It was found that the A' vibrational modes intensities maxima occur at a more negative potential than those of the A'' vibrational modes. Similar behavior was observed as the concentration of the supporting electrolyte was varied. These results were interpreted in terms of a geometric electrostatic effect of the chloride ions. A quantum mechanical calculation was then done to fit the data for the effect of electrode potential on the intensities of different modes of piperidine. Also the effect on the SERS spectrum of the nature of the supporting electrolyte and the solvent was studied. A broad band at 965 cm('-1) in the SERS spectrum of piperidine/KCl-H(,2)O system shifts to 758 cm('-1) when the solvent is D(,2)O and also shows a strong dependency on the applied potential but not on the type of supporting electrolyte. The appearance of this new line is evidence of the participation of the solvent in a surface complex. The effects of the ionic strength of the solution on the SERS experiment was also studied. It was anticipated that molecules which are inactive in SERS would show SERS spectrum for sufficiently high supporting electrolyte concentration. This expectation was confirmed by observation of SERS spectra of ammonia, and suggests the importance of solvation in SERS. Finally, the SERS spectra of S-triazine, pyrrolidine, imidazol and trimethylamine and the potential dependence of these molecules were reported.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
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Program
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Chemistry
