Unified Description of Proton NMR Relaxation in Water, Acetonitrile, and Methane from Molecular Dynamics Simulations in the Liquid, Supercritical, and Gas Phases.

A comprehensive calculation of proton NMR relaxation in water, acetonitrile, and methane across a wide range of the phase diagram is provided via ab initio and force-field-based molecular dynamics simulations. The formalism used for the spin-rotation (SR) contribution to relaxation is developed for use with any molecular symmetry and utilizes the full molecular SR tensors, which are calculated from first-principles via Kohn-Sham (KS) DFT. In combination with calculations of the dipolar contribution, near-quantitative agreement with total measured relaxation rates is achieved.