Molecular dynamics simulations of NMR relaxation and diffusion of bulk hydrocarbons and water

Singer, Philip M.; Asthagiri, Dilip; Chapman, Walter G.; Hirasaki, George J.

doi:10.1016/j.jmr.2017.02.001

Molecular dynamics simulations of NMR relaxation and diffusion of bulk hydrocarbons and water

Journal Article · Fri Feb 03 00:00:00 EST 2017 · Journal of Magnetic Resonance

DOI:https://doi.org/10.1016/j.jmr.2017.02.001· OSTI ID:1543565

Singer, Philip M. ^[1]; Asthagiri, Dilip ^[1]; Chapman, Walter G. ^[1]; Hirasaki, George J. ^[1]

Rice Univ., Houston, TX (United States)

Molecular dynamics (MD) simulations are used to investigate ¹H nuclear magnetic resonance (NMR) relaxation and diffusion of bulk n-C₅H₁₂ to n-C₁₇H₃₆ hydrocarbons and bulk water. The MD simulations of the 1H NMR relaxation times T_1,2 in the fast motion regime where T₁ = T₂ agree with measured (de-oxygenated) T2 data at ambient conditions, without any adjustable parameters in the interpretation of the simulation data. Likewise, the translational diffusion DT coefficients calculated using simulation con gurations are well-correlated with measured diffusion data at ambient conditions. The agreement between the predicted and experimentally measured NMR relaxation times and diffusion coefficient also validate the force elds used in the simulation. The molecular simulations naturally separate intramolecular from intermolecular dipole-dipole interactions helping bring new insight into the two NMR relaxation mechanisms as a function of molecular chain-length (i.e. carbon number). Comparison of the MD simulation results of the two relaxation mechanisms with traditional hard-sphere models used in interpreting NMR data reveals important limitations in the latter. With increasing chain length, there is substantial deviation in the molecular size inferred on the basis of the radius of gyration from simulation and the tted hard-sphere radii required to rationalize the relaxation times. This deviation is characteristic of the local nature of the NMR measurement, one that is well-captured by molecular simulations.

View Accepted Manuscript (DOE)

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:: 1543565

Alternate ID(s):: OSTI ID: 1416639

Journal Information:: Journal of Magnetic Resonance, Journal Name: Journal of Magnetic Resonance Journal Issue: C Vol. 277; ISSN 1090-7807

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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