Differentiated adsorption of thiobenzoic acid and thiobenzamide on silver nanoparticles determined by SERS spectroscopy.

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2020
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Abstract
Surface-enhanced Raman scattering of thiobenzoic acid and thiobenzamide have been recorded on three different silver colloids in order to find the chemical species responsible for the spectra and to detect differences in the adsorption with respect to their oxygen counterparts, benzoic acid and benzamide, respectively. Very significant and unexpected shifts of opposite sign between the Raman and SERS wavenumbers have been detected. By comparing the experimental and DFT calculated wavenumbers, it can be concluded that the acid is bonded to the metal as thiobenzoate through the sulfur atom with unidentate coordination. SERS spectra of thiobenzamide can be explained by assuming that it is adsorbed as azanion, like in the case of benzamide, linking to the metal through the sulfur and nitrogen atoms of the ionized thiocarboxamide group. In order to support these conclusions, B3LYP/LanL2DZ force field calculations for different complexes of silver cations with the thiobenzoate anion, the neutral thiobenzamide as well as its azanion have been carried out. Additionally, the 8a;ν mode is the most enhanced band in the SERS of both adsorbates pointing to the participation of a metal-to-molecule resonant charge transfer mechanism.
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lpezramrez2020differentiatedspectrochimica Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors López-Ramírez, María Rosa;Aranda, Daniel;López-Tocón, Isabel;Soto, Juan;Castro, José Luis;Otero, Juan Carlos;
Journal spectrochimica acta part a, molecular and biomolecular spectroscopy
Year 2020
DOI
S1386-1425(20)31027-1
URL
Keywords
adsorption DFT sers raman benzamide benzoic silver sol thiobenzamide thiobenzoic

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