A QUANTUM CHEMISTRY GIAO MOLECULAR SITE APPROACH OF NMR CHEMICAL SHIFTS GENERALIZED TO THE WHOLE PERIODIC TABLE

Abstract

An accurate and rapid quantum chemistry approach to predicting chemical shifts is applied to 15 N natural abundance NMR spectra of benzothiazoles. This method is of interest in the study of toxic contaminants of biological media. A GIAO approach is used to calculate the nuclear shielding tensor in a perturbational scheme. Similar methods had previously been used for both ab initio and semi-empirical calculations programmed in Gaussian and MOPAC respectively but atomic orbitals specific to molecular sites are shown to improve accuracy in the present work. Some molecular sites are defined in order to polarize the molecular orbitals in the presence of the solvent interactions. For convenience, the extensions are carried out in an independent NMR module designed to work with the MOPAC package and the present application is generalized to the third row elements for the first time. This new theoretical work is described. The application to 15 N chemical shifts for benzothiazoles led to results within 0.5 ppm of values measured in this work. Structural investigations were carried out using the Gaussian98 suite of programs at the DFT B3LYP level of calculation over an extended basis set. These studies show the single chemical shift for benzothiazoles could be the result of rapid tautomeric equilibria. Further investigations show that solvent interactions involving hydrogen bonds should also be taken into account.