Identifying the structure of 4-chlorophenyl isocyanide adsorbed on Au(111) and Pt(111) surfaces by first-principles simulations of Raman spectra

Surface Raman spectroscopy has become one of the most powerful analytical tools for interfacial structures. However, theoretical modeling for the Raman spectra of molecular adsorbate on metallic surfaces is a long-standing challenge because accurate descriptions of the electronic structure for both the metallic substrates and adsorbates are required. Here we present a quasi-analytical method for high-precision surface Raman spectra at the first principle level. Using this method, we correlate both geometrical and electronic structures of a single 4-chlorophenyl isocyanide (CPI) molecule adsorbed on a Au(111) or Pt(111) surface with its Raman spectra. The “finger-print” frequency shift of the CN stretching mode reveals the in situ configuration of CPI is vertical adsorption on the top site of the Au(111) surface, but a bent configuration when it adsorbs on the hollow site of the Pt(111) surface. Electronic structure calculations reveal that a π-back donation mechanism often causes a red shift to the Raman response of CN stretching mode. In contrast, σ donation as well as a wall effect introduces a blue shift to the CN stretching mode. A clear relationship for the dependence of Raman spectra on the surface electronic and geometrical information is built up, which largely benefits the understanding of chemical and physical changes during the adsorption. Our results highlight that high-precision theoretical simulations are essential for identifying in situ geometrical and electronic surface structures.