Systematic discrepancy of theoretical predictions of NMR chemical shifts for chlorinated aromatic carbons using the GIAO DFT method

Abstract

Theoretical calculations of carbon-13 NMR chemical shifts using the gauge including atomic orbitals (GIAO) DFT approach with a moderately large set of basis functions usually yield quite satisfactory results. In the case of chlorinated aromatic carbons, however, abnormally large differences between experimental and calculated values have been noticed. This discrepancy has been proven not to be caused by improper referencing, or the basis set effect, and probably not by neglect of vibrational corrections. One of the possible sources of the chlorine effect could be the impact of relativistic phenomena on electrons moving about the chlorine nucleus. The second, probably more important factor is the influence of electron correlations, ignored in Hartree–Fock SCF and only partially included in DFT calculations. Surprisingly, however, the observed divergence has been significantly larger for DFT than for Hartree–Fock results. In the latter case the observed divergence between theoretical and experimental 13C NMR chemical shifts of chlorine-bonded carbons is systematic but rather small (3.4–4.4ppm).