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Title: NMR spin-rotation relaxation and diffusion of methane

Abstract

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 1Hmore » spin-rotation relaxation, without any adjustable parameters.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Rice Univ., Houston, TX (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543861
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 20; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Singer, P. M., Asthagiri, D., Chapman, W. G., and Hirasaki, G. J. NMR spin-rotation relaxation and diffusion of methane. United States: N. p., 2018. Web. doi:10.1063/1.5027097.
Singer, P. M., Asthagiri, D., Chapman, W. G., & Hirasaki, G. J. NMR spin-rotation relaxation and diffusion of methane. United States. doi:https://doi.org/10.1063/1.5027097
Singer, P. M., Asthagiri, D., Chapman, W. G., and Hirasaki, G. J. Tue . "NMR spin-rotation relaxation and diffusion of methane". United States. doi:https://doi.org/10.1063/1.5027097. https://www.osti.gov/servlets/purl/1543861.
@article{osti_1543861,
title = {NMR spin-rotation relaxation and diffusion of methane},
author = {Singer, P. M. and Asthagiri, D. and Chapman, W. G. and Hirasaki, G. J.},
abstractNote = {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.},
doi = {10.1063/1.5027097},
journal = {Journal of Chemical Physics},
number = 20,
volume = 148,
place = {United States},
year = {2018},
month = {5}
}

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