Journal
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume 16, Issue 7, Pages 3153-3161Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3cp54856b
Keywords
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Funding
- National Natural Science Foundation of P. R. China [20921003, 20973074]
- Specialized Research Fund for the Doctoral Program of Higher Education [20110061110017]
- 111 project [B06009]
- Development Program of the Science and Technology of Jilin Province [20110338]
- Grants-in-Aid for Scientific Research [13F03332] Funding Source: KAKEN
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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 b(2)-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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