Prediction of $^1$H singlet relaxation via intermolecular dipolar couplings using the molecular dynamics method

TL;DR

This paper predicts the relaxation times of proton nuclear singlet states using molecular dynamics and quantum chemistry, considering various interactions, to aid in designing NMR applications and understanding spin relaxation.

Contribution

It introduces a method combining molecular dynamics and quantum chemistry to predict proton singlet relaxation times, including intermolecular dipolar effects, with results comparable to experiments.

Findings

Calculated relaxation rates match experimental values in order of magnitude.

Intermolecular dipolar interactions significantly influence singlet relaxation times.

The method aids in molecular design for NMR applications.

Abstract

Dissolution dynamical nuclear polarization has been applied in various fields, including chemistry, biology, and medical science. To expand the scope of these applications, the nuclear singlet state, which is decoherence-free against dipolar relaxation between spin pairs, has been studied experimentally, theoretically, and numerically. The singlet state composed of proton spins is used in several applications, such as enhanced polarization preservation, molecular tag to probe slow dynamic processes, and detection of ligand--protein complexes. In this study, we predict the lifetimes of the nuclear spin states composed of proton spin pairs using the molecular dynamics method and quantum chemistry simulations. We consider intramolecular and intermolecular dipolar, chemical shift anisotropy, and spin--rotation interactions. In particular, the relaxation rate of intermolecular dipolar interactions is calculated using the molecular dynamics method for various solvents. The calculated values and the experimental values are of the same order of magnitude. Our program would provide insight into the molecular design of several NMR applications and would be helpful in predicting the nuclear spin relaxation time of synthetic molecules in advance.