A molecular dynamics study of natural organic matter: 1. Lignin, kerogen and soot

Abstract

Molecular dynamics (MD) simulations were performed on molecular models of a spectrum of natural organic matter (NOM) samples represented by two lignin samples (a softwood lignin and a hardwood lignin), a kerogen (Green River Shale kerogen) and a soot sample ( n-hexane soot). Simulated thermodynamic properties of each model, including glass transition temperature ( T g ), thermal expansion coefficient ( α), density ( ρ) and solubility parameter ( δ) were compared against experimental data for corresponding samples. Results revealed relatively good agreement for glass transition temperature and solubility parameter for softwood lignin, Green River Shale kerogen and n-hexane soot models. An unexpectedly low solubility parameter for a hardwood lignin model suggests, however, certain model deficiencies in terms of intermolecular interactions. In addition, a lower density for a n-hexane soot model relative to the sample was attributed to the small cluster size and poor parallel stacking of aromatic clusters in the model. Discussion of the results is provided in the context of utilizing thermodynamic properties as constraints for improved structural modeling of NOM.