To illustrate the performance of the SQC/MM-DW methodology, we chose two well-known molecules, cis-azobenzene and cis-hepta-3,5,7-trieniminium cation (PSB4), which are sketched in Fig. (a) and (b). Optimizations of the S 0 minima of both systems were performed by employing the complete active space self-consistent field (CASSCF) in the Gaussian 16 package where azobenzene is optimized at CASSCF(6,6)/6-31G level while PSB4 at CASSCF(8,8)/6-31G(d). In the on-the-fly SQC/MM dynamics simulations, the MOLPRO2022 package 118 was used for the electronic structures calculations.