Geometric dependence of the B3LYP-Predicted magnetic shieldings and chemical shifts

Abstract

We perform a systematic investigation of how the B3LYP/6-311+G(2d,p) calculated C-13 nuclear magnetic shielding constants depend on the 6-31G(d)-optimized geometries for a set of 18 molecules with various chemical environments. For absolute shieldings, the Hartree-Fock (HF)-optimized geometries lead to a mean absolute deviation (MAD) of 5.65 ppm, while the BLYP- and B3LYP-optimized geometries give MADs of 13.07 and 10.14 ppm, respectively. For chemical shifts, the HF, BLYP and B3LYP geometries lead to MADs of 2.36, 5.80, and 4.43 ppm, respectively. We find that the deshielding tendency of B3LYP can be effectively compensated by using the HF-optimized geometries. When we apply the B3LYP//HF protocol to versicolorin A and 5 alpha-androstan-3,17-dione, MADs of 1.86 and 1.41 ppm, respectively, are obtained for chemical shifts, in satisfactory agreement with the experiment.