Combining ab initio and density functional theories with semiempirical methods

For large reactive systems, the calculation of energies can be simplified by treating the active part with a high-level quantum mechanical (QM) (ab initio or density functional) approach and the environment with a less sophisticated semiempirical (SE) approach, as an improvement over the widely used hybrid quantum mechanical/molecular mechanical (QM/MM) methods. An example is the interaction between an active region of an enzyme and its immediate environment. One such method is the original “Our-own-N-layer Integrated molecular Orbital+Molecular Mechanics (ONIOM)” approach. In this paper, the interaction between the QM and SE region is described explicitly by two different schemes. In the iterative QM/SE schemes (QM/SE-I), the electrostatic interaction and polarization effects are introduced explicitly for both the QM and SE atoms by a self-consistent procedure based on either polarizable point charges or the electron density. In the noniterative QM/SE scheme, based on the ONIOM model (QM/SE-O), the excha...

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