Solvent effects on nuclear shieldings and spin–spin couplings of hydrogen selenide

Abstract

Solvent effects on the nuclear shielding and indirect spin–spin coupling constants of H2Se have been calculated by modeling the surroundings as a continuous dielectric medium. Gauge-origin independence of the nuclear shieldings is ensured by using London atomic orbitals in combination with linear response theory. We present the linear response function of a solvated molecule subject to triplet perturbations and use a new implementation of this theory to evaluate the Fermi-contact and spin–dipole contributions to the indirect spin–spin coupling constants. We present high-level calculations of the nuclear shielding and indirect spin–spin coupling constants of H2Se in vacuum and different solvents. Our results represent the first ab initio calculations of the spin–spin coupling constants in H2Se as well as the first investigation of medium effects on these properties. It is demonstrated that the solvent shifts of the spin–spin couplings are caused by a polarization of the molecular electronic structure as well as by changes in the geometry upon solvation.