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

PM Singer and D Asthagiri and Z Chen and AV Parambathu and GJ Hirasaki and WG Chapman, JOURNAL OF CHEMICAL PHYSICS, 148, 164507 (2018).

DOI: 10.1063/1.5023240

The role of internal motions and molecular geometry on H-1 NMR relaxation rates in liquid-state hydrocarbons is investigated using MD (molecular dynamics) simulations of the autocorrelation functions for intramolecular and intermolecular H-1-H-1 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 significantly smaller, especially for longer-chain n-alkanes. Site-by-site simulations of H-1'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. Furthermore, 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. Published by AIP Publishing.

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