Critical Role of Confinement in the NMR Surface Relaxation and Diffusion of n‑Heptane in a Polymer Matrix Revealed by MD Simulations

The mechanism behind the NMR surface-relaxation times (T 1S,2S) and the large T 1S/T 2S ratio of light hydrocarbons confined in the nanopores of kerogen remains poorly understood and consequently has engendered much debate. Toward bringing a molecular-scale resolution to this problem, we present molecular dynamics (MD) simulations of 1H NMR relaxation and diffusion of n-heptane in a polymer matrix. The high-viscosity polymer is a model for kerogen and bitumen that provides an organic “surface” for heptane. Diffusion of n-heptane shows a power-law dependence on the concentration of n-heptane (ϕC7) in the polymer matrix, consistent with Archie’s model of tortuosity. We calculate the autocorrelation function G(t) for 1H–1H dipole–dipole interactions of n-heptane in the polymer matrix and use this to generate the NMR frequency (f 0) dependence of T 1S,2S as a function of ϕC7. We find that increasing molecular confinement increases the correlation time, which decreases the surface-relaxation times for n-heptane in the polymer matrix. For weak confinement (ϕC7 > 50 vol %), we find that T 1S/T 2S ≃ 1. Under strong confinement (ϕC7 ≲ 50 vol %), we find that T 1S/T 2S ≳ 4 increases with decreasing ϕC7 and that the dispersion relation T 1S ∝ f 0 is consistent with previously reported measurements of polydisperse polymers and bitumen. Such frequency dependence in bitumen has been previously attributed to paramagnetism; instead, our studies suggests that 1H–1H dipole–dipole interactions enhanced by organic nanopore confinement dominate the NMR response in saturated organic-rich shales.