Effects of Au6 and Au20 Adsorption Sites of Cyromazine–Au Complexes by Raman Spectroscopy and Density Functional Theory

Cyromazine, when used as an insect growth regulator and low-toxicity insecticide, may degrade into melamine and pose a potential threat to the environment and soil health, which has thus attracted extensive research on eliminating such a harmful effect. In this paper, density functional theory (DFT)/LC-BLYP/6-311G(d,p) is used to optimize the geometric structure and analyze the vibration of cyromazine. The DFT/LC-BLYP/def2-SVP is used for the cyromazine–Au complex optimization and vibration analysis. The molecular electrostatic potential (MEP), frontier molecular orbitals (FMOs), vibration frequency, electrophilicity-based charge transfer (ECT) descriptor, binding energy (BE), polarizability, normal Raman spectroscopy (NRS), and surface-enhanced Raman spectroscopy (SERS) of cyromazine adsorbing on Au6 and Au20 are calculated. The study of the chemical enhancement mechanism of SERS of cyromazine at different adsorption sites of Au6 or Au20 confirms the existence of a charge transfer between cyclopromazine and Au6 and Au20, which can adsorb and form stable cyromazine–Au complexes. The results show that N2, H13, and N4 are the adsorption sites of Au6 and Au20. The Raman spectra of the cyromazine–Au complex can be selectively enhanced with a factor up to 9.07. Compared with those of cyromazine–Au6, the Raman spectra of cyromazine–Au20 are enhanced more significantly.