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ABSTRACT:The structure and electronic properties of the Brønsted acid site in B, Al or Ga isomorphously substituted ZSM-5 zeolites were studied by using quantum cluster and embedded ONIOM approaches. In the former approach, zeolites are modeled by 5T and 12T quantum clusters, where T represents a Si or Al atom. In the latter model, called ''Embedded ONIOM'', the long-range interactions of the zeolite lattice beyond the 12T quantum cluster is included via optimized point charges added to the ONIOM(B3LYP/6-31G(d,p):UFF). Inclusion of the extended zeolitic framework covering the nanocavity has an effect on the structure and adsorption properties. We found that the OH distances and v OH of the acidic proton in zeolite obtained from both models can predict the trend of acid strength as: B-ZSM-5 < Ga-ZSM-5 < Al-ZSM-5, which is in very good agreement with the experimental sequence. Furthermore, the PA data calculated from E-ONIOM is also consistent with the experimental trend: B-ZSM-5 < Ga-ZSM-5 < Al-ZSM-5. It has, therefore, been demonstrated that our embedded ONIOM model provides accurate performance and can be one of the useful and affordable methods for future mechanistic studies involving petrochemical reactions.