$^1$H-NMR Dipole-Dipole Relaxation in Fluids: Relaxation of Individual $^1$H-$^1$H Pairs versus Relaxation of Molecular Modes

TL;DR

This study uses molecular dynamics simulations to challenge traditional BPP theory in describing intra- and inter-molecular $^1$H-$^1$H dipole-dipole relaxation, revealing complex behaviors and proposing a mode-based analysis.

Contribution

It demonstrates that $^1$H-$^1$H autocorrelation functions are not mono-exponential and introduces a mode expansion approach to better understand relaxation dynamics.

Findings

Autocorrelation functions exhibit stretched-exponential behavior.

Molecular symmetry influences agreement with BPP theory.

Mode expansion can recover molecular mode distributions.

Abstract

The intra-molecular $^1$H-NMR dipole-dipole relaxation of molecular fluids has traditionally been interpreted within the Bloembergen-Purcell-Pound (BPP) theory of NMR intra-molecular relaxation. The BPP theory draws upon Debye's theory for describing the rotational diffusion of the $^1$H-$^1$H pair and predicts a mono-exponential decay of the $^1$H-$^1$H dipole-dipole autocorrelation function between distinct spin pairs. Using molecular dynamics (MD) simulations, we show that for both $n$-heptane and water this is not the case. In particular, the autocorrelation function of individual $^1$H-$^1$H intra-molecular pairs itself evinces a rich stretched-exponential behavior, implying a distribution in rotational correlation times. However for the high-symmetry molecule neopentane, the individual $^1$H-$^1$H intra-molecular pairs do conform to the BPP description, suggesting an important role of molecular symmetry in aiding agreement with the BPP model. The inter-molecular autocorrelation functions for $n$-heptane, water, and neopentane also do not admit a mono-exponential behavior of individual $^1$H-$^1$H inter-molecular pairs at distinct initial separations. We suggest expanding the auto-correlation function in terms of molecular modes, where the molecular modes do have an exponential relaxation behavior. With care, the resulting Fredholm integral equation of the first kind can be inverted to recover the probability distribution of the molecular modes. The advantages and limitations of this approach are noted.