Quadrupolar NMR Relaxation of Aqueous 127I-, 131Xe, and 133Cs+: A First-Principles Approach from Dynamics to Properties.

Quadrupolar NMR relaxation rates were computed for aqueous 133Cs+, 131Xe, and 127I- via Kohn-Sham (KS) density functional theory-based ab initio molecular dynamics and KS calculations of the electric field gradient (EFG) tensors along the trajectories. The resulting rates are within a factor of 1-3 of the experimental values and can be compared to available results from classical dynamics and EFGs from electrostatic models with corrections via Sternheimer antishielding factors. Relativistic effects are shown to have an enhancing effect on the magnitude of the EFGs. An analysis of the EFGs was carried out in terms of localized molecular orbitals to elucidate contributions from the solvent versus solute polarization and assess the validity of the Sternheimer approximation for these systems.