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Title: Role of internal motions and molecular geometry on the NMR relaxation of hydrocarbons

Abstract

The role of internal motions and molecular geometry on 1H NMR relaxation rates in liquid-state hydrocarbons is investigated using MD (molecular dynamics) simulations of the autocorrelation functions for intramolecular and intermolecular 1H– 1H dipole-dipole interactions. The effects of molecular geometry and internal motions on the functional form of the autocorrelation functions are studied by comparing symmetric molecules such as neopentane and benzene to corresponding straight-chain alkanes n-pentane and n-hexane, respectively. Comparison of rigid versus flexible molecules shows that internal motions cause the intramolecular and intermolecular correlation-times to get significantly shorter, and the corresponding relaxation rates to get increasingly smaller, especially for longer-chain n-alkanes. Site-by-site simulations of 1H’s across the chains indicate significant variations in correlation times and relaxation rates across the molecule, and comparison with measurements reveals insights into cross-relaxation effects. Moreover, the simulations reveal new insights into the relative strength of intramolecular versus intermolecular relaxation as a function of internal motions, as a function of molecular geometry, and on a site-by-site basis across the chain.

Authors:
ORCiD logo [1]; ORCiD logo [1]; 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:
1543856
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 16; 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

Citation Formats

Singer, P. M., Asthagiri, D., Chen, Z., Valiya Parambathu, A., Hirasaki, G. J., and Chapman, W. G. Role of internal motions and molecular geometry on the NMR relaxation of hydrocarbons. United States: N. p., 2018. Web. doi:10.1063/1.5023240.
Singer, P. M., Asthagiri, D., Chen, Z., Valiya Parambathu, A., Hirasaki, G. J., & Chapman, W. G. Role of internal motions and molecular geometry on the NMR relaxation of hydrocarbons. United States. doi:10.1063/1.5023240.
Singer, P. M., Asthagiri, D., Chen, Z., Valiya Parambathu, A., Hirasaki, G. J., and Chapman, W. G. Mon . "Role of internal motions and molecular geometry on the NMR relaxation of hydrocarbons". United States. doi:10.1063/1.5023240. https://www.osti.gov/servlets/purl/1543856.
@article{osti_1543856,
title = {Role of internal motions and molecular geometry on the NMR relaxation of hydrocarbons},
author = {Singer, P. M. and Asthagiri, D. and Chen, Z. and Valiya Parambathu, A. and Hirasaki, G. J. and Chapman, W. G.},
abstractNote = {The role of internal motions and molecular geometry on 1H NMR relaxation rates in liquid-state hydrocarbons is investigated using MD (molecular dynamics) simulations of the autocorrelation functions for intramolecular and intermolecular 1H–1H dipole-dipole interactions. The effects of molecular geometry and internal motions on the functional form of the autocorrelation functions are studied by comparing symmetric molecules such as neopentane and benzene to corresponding straight-chain alkanes n-pentane and n-hexane, respectively. Comparison of rigid versus flexible molecules shows that internal motions cause the intramolecular and intermolecular correlation-times to get significantly shorter, and the corresponding relaxation rates to get increasingly smaller, especially for longer-chain n-alkanes. Site-by-site simulations of 1H’s across the chains indicate significant variations in correlation times and relaxation rates across the molecule, and comparison with measurements reveals insights into cross-relaxation effects. Moreover, the simulations reveal new insights into the relative strength of intramolecular versus intermolecular relaxation as a function of internal motions, as a function of molecular geometry, and on a site-by-site basis across the chain.},
doi = {10.1063/1.5023240},
journal = {Journal of Chemical Physics},
number = 16,
volume = 148,
place = {United States},
year = {2018},
month = {4}
}

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