Dietmar Paschek

We present a computational framework for reliably determining the frequency-dependent intermolecular and intramolecular nuclear magnetic resonance (NMR) dipole–dipole relaxation rates of spin 1/2 nuclei from Molecular Dynamics (MD) simulations. This approach avoids the alterations caused by the well-known finite-size effects of translational diffusion. Moreover, a procedure is derived to control and correct for effects caused by fixed distance-sampling cutoffs and periodic boundary conditions. By construction, this approach is capable of accurately predicting the correct low-frequency scaling behavior of the intermolecular NMR dipole–dipole relaxation rate and thus allows for the reliable calculation of the frequency-dependent relaxation rate over many orders of magnitude. Our approach is based on the utilization of the theory of Hwang and Freed for the intermolecular dipole–dipole correlation function and its corresponding spectral density [L.-P. Hwang and J. H. Freed, J. Chem. Phys. 63, 4017–4025 (1975)] and its combination with data from MD simulations. The deviations from the Hwang and Freed theory caused by periodic boundary conditions and sampling distance cutoffs are quantified by means of random walker Monte Carlo simulations. An expression based on the Hwang and Freed theory is also suggested for correcting those effects. As a proof of principle, our approach is demonstrated by computing the frequency-dependent intermolecular and intramolecular dipolar NMR relaxation rates of 1H nuclei in liquid water at 273 and 298 K based on the simulations of the TIP4P/2005 model. Our calculations are suggesting that the intermolecular contribution to the 1H NMR relaxation rate of the TIP4P/2005 model in the extreme narrowing limit has previously been substantially underestimated.