NMR spin–spin coupling constants in microhydrated ortho-aminobenzoic acid

Abstract

The influence of the hydrogen-bond formation on the NMR spin–spin coupling constants, including the Fermi contact, the diamagnetic spin–orbit, the paramagnetic spin–orbit and the spin dipole term, has been investigated for the ortho-aminobenzoic acid microhydrated with up to three water molecules. The one-bond and two-bond spin–spin coupling constants for several intra-molecular and across-the-hydrogen-bond atomic pairs are calculated employing high-level density functional theory in combination with the B3LYP functional with two different types of extended basis sets for each level of microhydration. The spin–spin coupling constants, in general, vary inversely with the hydrogen bond length. The Fermi contact term is found to be the dominant contributor to the total value of spin–spin coupling constant followed by the paramagnetic spin–orbit term. The variations of Fermi contact term and atomic charge distribution with size of microhydration follow quite similar trend. The effect of explicit solvation provided by microhydration has also been compared briefly with that of bulk implicit solvation obtained through polarised continuum model and mixed microhydration/continuum approach.