Molecular Modes Elucidate the Nuclear Magnetic Resonance Relaxation of Viscous Fluids

Valiya Parambathu, Arjun; Pinheiro dos Santos, Thiago J.; Chapman, Walter G.; Hirasaki, George J.; Asthagiri, Dilipkumar N.; Singer, Philip M.

doi:10.1021/acs.jpcb.4c02631

Molecular Modes Elucidate the Nuclear Magnetic Resonance Relaxation of Viscous Fluids

Journal Article · Fri Aug 09 00:00:00 EDT 2024 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.4c02631· OSTI ID:2429825

^[1]; Pinheiro dos Santos, Thiago J. ^[2]; ^[2]; Hirasaki, George J. ^[2]; ^[3]; ^[2]

Rice Univ., Houston, TX (United States); Univ. of Delaware, Newark, DE (United States)
Rice Univ., Houston, TX (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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 T₁ 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 T₁ 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 T₁ 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.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231; AC05-00OR22725

OSTI ID:: 2429825

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 33 Vol. 128; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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