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When p-aminothiophenol (PATP) is used as a probe molecule and adsorbs on silver and gold nanogaps, a significant change of relative SERS intensities can be observed. Our DFT calculations show that surface photocatalytic coupling reactions yield a new surface species of p,p′-dimercaptoazobenzene (DMAB) causing the significant change in the SERS spectra.

Graphical abstract: Photon-driven charge transfer and photocatalysis of p-aminothiophenol in metal nanogaps: a DFT study of SERS

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