Molecular Modes Elucidate the Nuclear Magnetic Resonance Relaxation of Viscous Fluids

• Published in: The journal of physical chemistry. B Vol. 128; no. 33; pp. 8017 - 8028
• Main Authors: Valiya Parambathu, Arjun, Pinheiro dos Santos, Thiago J., Chapman, Walter G., Hirasaki, George J., Asthagiri, Dilipkumar N., Singer, Philip M.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 22-08-2024
• Subjects: Alcohols; B: Liquids; Chemical and Dynamical Processes in Solution; colloids; molecules; nuclear magnetic resonance spectroscopy; viscosity
• ISSN: 1520-6106; 1520-5207; 1520-5207
• DOI: 10.1021/acs.jpcb.4c02631

The Bloembergen, Purcell, and Pound (BPP) theory of nuclear magnetic resonance (NMR) relaxation in fluids dating back to 1948 continues to be the linchpin in interpreting NMR relaxation data in applications ranging from characterizing fluids in porous media to medical imaging (MRI). The BPP theory is founded on assuming molecules are hard spheres with 1H–1H dipole pairs reorienting randomly; assumptions that are severe in light of modern understanding of liquids. Nevertheless, it is intriguing to this day that the BPP theory was consistent with the original experimental data for glycerol, a hydrogen-bonding molecular fluid for which the hard-sphere-rigid-dipole assumption is inapplicable. To better understand this incongruity, atomistic molecular simulations are used to compute 1H NMR T 1 relaxation dispersion (i.e., frequency dependence) in two contrasting cases: glycerol, and a (non hydrogen-bonding) viscosity standard. At high viscosities, simulations predict distinct functional forms of T 1 for glycerol compared to the viscosity standard, in agreement with modern measurements, yet both in contrast to BPP theory. The cause of these departures from BPP theory is elucidated, without assuming any relaxation models and without any free parameters, by decomposing the simulated T 1 response into dynamic molecular modes for both intramolecular and intermolecular interactions. The decomposition into dynamic molecular modes provides an alternative framework to understand the physics of NMR relaxation for viscous fluids.