When Theory Meets Experiment: What Does it Take to Accurately Predict $^1$H NMR Dipolar Relaxation Rates in Neat Liquid Water from Theory?

TL;DR

This study combines high-accuracy quantum chemistry, nuclear quantum effects, and experimental data to accurately predict $^1$H NMR relaxation rates in liquid water, achieving near-perfect agreement with experiments.

Contribution

It introduces a computational framework that effectively disentangles structural and dynamical contributions to NMR relaxation rates, incorporating quantum effects and finite-size corrections.

Findings

Quantum effects significantly alter water's rotational and translational dynamics.

Intermolecular and intramolecular contributions to relaxation are nearly equal.

The approach achieves near-perfect agreement with experimental relaxation data.

Abstract

In this contribution, we compute the $^1$H nuclear magnetic resonance (NMR) relaxation rate of liquid water at ambient conditions. We are using structural and dynamical information from Coupled Cluster Molecular Dynamics (CCMD) trajectories generated at CCSD(T) electronic structure accuracy while considering also nuclear quantum effects in addition to consulting information from X-ray and neutron scattering experiments. Our analysis is based on a recently presented computational framework for determining the frequency-dependent NMR dipole-dipole relaxation rate of spin $1/2$ nuclei from Molecular Dynamics (MD) simulations, which allows for an effective disentanglement of its structural and dynamical contributions, and is including a correction for finite-size effects inherent to MD simulations with periodic boundary conditions. A close to perfect agreement with experimental relaxation data is achieved if structural and dynamical informations from CCMD trajectories are considered including a re-balancing of the rotational and translational dynamics, according to the product of the self-diffusion coefficient and the reorientational correlation time of the H-H vector $D_0\times\tau_\mathrm{HH}$. The simulations show that this balance is significantly altered when nuclear quantum effects are taken into account. Our analysis suggests that the intermolecular and intramolecular contribution to the $^1$H NMR relaxation rate of liquid water are almost similar in magnitude, unlike to what was predicted earlier from classical MD simulations.