Molecular dynamics simulations of NMR relaxation and diffusion of bulk hydrocarbons and water

Molecular dynamics (MD) simulations are used to investigate ¹H nuclear magnetic resonance (NMR) relaxation and diffusion of bulk n-C₅H₁₂ to n-C₁₇H₃₆ hydrocarbons and bulk water. The MD simulations of the ¹H NMR relaxation times T_1,2 in the fast motion regime where T₁=T₂ agree with measured (de-oxygenated) T₂ data at ambient conditions, without any adjustable parameters in the interpretation of the simulation data. Likewise, the translational diffusion D_T coefficients calculated using simulation configurations agree with measured diffusion data at ambient conditions. The agreement between the predicted and experimentally measured NMR relaxation times and diffusion coefficient also validate the forcefields used in the simulation. The molecular simulations naturally separate intramolecular from intermolecular dipole-dipole interactions helping bring new insight into the two NMR relaxation mechanisms as a function of molecular chain-length (i.e. carbon number). Comparison of the MD simulation results of the two relaxation mechanisms with traditional hard-sphere models used in interpreting NMR data reveals important limitations in the latter. With increasing chain length, there is substantial deviation in the molecular size inferred on the basis of the radius of gyration from simulation and the fitted hard-sphere radii required to rationalize the relaxation times. This deviation is characteristic of the local nature of the NMR measurement, one that is well-captured by molecular simulations.