Abstract

The ab initio calculation of 33 S nuclear quadrupole coupling constants (NQCC) for a range of S-containing compounds with S 2 , S 4 and S 6 bonding types is described. All of the calculations used a triple zeta valence + polarisation basis set (TZVP) of gaussian type orbitals; all of the molecules were studied at the TZVP equilibrium geometry. The electric field gradients (EFG) calculated were correlated with the experimental NQCC obtained by either microwave spectroscopy (MW), nuclear quadrupole resonance (NQR) or NMR relaxation methods; although the experimental data cover a wide diversity of chemical types over a long period of time, the slope of the relationship between the EFG (q u) and the NQCC (x u) yields a value for the 33 S atomic quadrupole moment of — 0.064 barn, very close to recent calculations with a large atomic basis set, and to experimental data. The relationship between the EFG tensor components and the internal molecular structure features is discussed for a diverse series of molecules.