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Phys Chem Chem Phys. 2014 Feb 21;16(7):3153-61. doi: 10.1039/c3cp54856b. Epub 2014 Jan 9.

Contribution of hydrogen bonding to charge-transfer induced surface-enhanced Raman scattering of an intermolecular system comprising p-aminothiophenol and benzoic acid.

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  • 1State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012, P. R. China. zhaob@mail.jlu.edu.cn.

Abstract

We investigated the influence of hydrogen bonds (H-bonds) on the intermolecular interactions of a system comprising p-aminothiophenol (PATP) and benzoic acid (BA) using surface-enhanced Raman scattering (SERS) for the first time. In this system, H-bonds form through intermolecular interactions between the -NH2 and -COOH groups and promote the charge-transfer (CT) transition from the Ag substrate to the adsorbed PATP molecules. Accordingly, the intensities of the non-totally symmetric vibrations (the b2-type bands) of PATP are influenced through the Herzberg-Teller contribution. This is clearly a BA concentration-dependent phenomenon. This behaviour can be attributed to an increase in the degree of conjugation of the system, which facilitates the CT process in the system with H-bonds. Furthermore, temperature-dependent SERS experiments and their two-dimensional (2D) correlation analysis confirmed that the formation of H-bonds facilitated the CT transition between the adsorbed molecules and substrate. The degree of CT was reduced by H-bond breakage that occurred with increasing temperature. An additional SERS experiment involving substituted BA molecules yielded similar conclusions.

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