ONIOM as an efficient tool for calculating NMR chemical shielding constants in large molecules

The ONIOM approach is used to derive an expression for the NMR chemical shielding tensor in a molecule subdivided into n-layers, each of which can be described at a different level of theory. The two-layer ONIOM2(MP2-GIAO:HF-GIAO) variant, in which a small part of the molecule containing the nuclei of interest is described at the MP2-GIAO level of theory, and the rest – using the HF-GIAO approach – is tested through calculations of absolute isotropic 13C, 17O, 19F, and proton NMR chemical shieldings in the water dimer, ethanol, acetone, acrolein, fluorobenzene, and naphthalene. The results show that with an appropriate partitioning this scheme furnishes shieldings which represent close approximations to the corresponding MP2-GIAO values for the entire molecule and offers a highly efficient tool for accurate shielding calculations on large molecules.