The paper is organized as follows. Section II briefly recaps the basic theoretical foundation of the polarizable QM/MM model for the ground-state energy of a molecule-MNP system and presents the analytical expressions for high-order derivatives of the energy with respect to the QM nuclear and field perturbations. It is followed by the computational details in Section III. In Section IV, using the pyridine molecule in the vicinity of three gold clusters as testing systems, the computed IR and Raman spectra are presented and discussed. In addition, the SERS of 4,4 -bipyridine on gold and silver MNPs are simulated by QM/DIM method and compared with experimental spectra. Moreover, the effects of nonlinear response of MNP and charge migration to Raman intensity are analysed. Finally, the concluding remarks and potential future improvements are summarized in the last section.