Multilayer cooperative chemisorption in surface-enhanced infrared absorption (SEIRA) spectroscopy

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The cooperative chemisorption of multilayers of 2,4-dinitrobenzoic acid on a silver surface under high vacuum was studied by microtransmission infrared spectrometry. The fact that the antisymmetric stretching modes of the carboxylate and nitro groups are active in the SEIRA spectra of 2,4- and 3,5-dinitrobenzoic acid suggests that the bottom layer is adsorbed perpendicular to the metal surface with higher layers oriented obliquely. Multilayer cooperative chemisorption and the effect of the solvent on the SEIRA spectra of p-nitrobenzoic acid (PNBA) were also observed. The symmetric COO- stretch in the SEIRA spectra of multilayers of PNBA is split into a doublet. Because there is a weaker interaction between the COO- group of PNBA in the upper layers with the Ag surface than for the bottom layers, we assign the 1420 cm-1 component to the symmetric COO- stretch of the upper layers of PNBA and the 1387 cm-1 band to the corresponding mode of the lower layers.

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