NMR spin-rotation relaxation and diffusion of methane

Singer, P. M.; Asthagiri, D.; Chapman, W. G.; Hirasaki, G. J.

doi:10.1063/1.5027097

Title: NMR spin-rotation relaxation and diffusion of methane

Journal Article · 21 May 2018 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5027097 · OSTI ID:1543861

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Rice Univ., Houston, TX (United States)

The translational diffusion-coefficient and the spin-rotation contribution to the ¹H NMR relaxation rate for methane (CH₄) are investigated using MD (molecular dynamics) simulations, over a wide range of densities and temperatures, spanning the liquid, supercritical, and gas phases. Here, the simulated diffusion-coefficients agree well with measurements, without any adjustable parameters in the interpretation of the simulations. A minimization technique is developed to compute the angular velocity for non-rigid spherical molecules, which is used to simulate the autocorrelation function for spin-rotation interactions. With increasing diffusivity, the autocorrelation function shows increasing deviations from the single-exponential decay predicted by the Langevin theory for rigid spheres, and the deviations are quantified using inverse Laplace transforms. The ¹H spin-rotation relaxation rate derived from the autocorrelation function using the “kinetic model” agrees well with measurements in the supercritical/gas phase, while the relaxation rate derived using the “diffusion model” agrees well with measurements in the liquid phase. ¹H spin-rotation relaxation is shown to dominate over the MD-simulated ¹H-¹H dipole-dipole relaxation at high diffusivity, while the opposite is found at low diffusivity. At high diffusivity, the simulated spin-rotation correlation time agrees with the kinetic collision time for gases, which is used to derive a new expression for ¹H spin-rotation relaxation, without any adjustable parameters.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1543861

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 148; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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