2020/06/10 by D. Asthagiri, Walter G. Chapman, Asthagiri, D. +5
Chemistry · Physics and Astronomy · #Advanced NMR Techniques and Applications #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Materials Science (cond-mat.mtrl-sci) #NMR spectroscopy and applications #Quantum, superfluid, helium dynamics
paper · pdf · doi:10.48550/arxiv.2006.06055
openalex publication_date 2020/06/10 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
The intra-molecular 1H-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 1H-1H pair and predicts a mono-exponential decay of the 1H-1H 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 1H-1H 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 1H-1H 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 1H-1H 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.