Coarse-Grained Molecular Dynamics Study of the Melting Dynamics in Long Alkanes.

Abstract

The melting behavior of alkanes plays a critical role in a wide field of applications. While experimental studies have established the occurrence of premelting phenomena in both short- and long-chain alkanes, molecular-level insights remain limited. In this work, we employ coarse-grained molecular dynamics simulations to investigate the melting behavior of high-molecular-weight alkanes, with a particular focus on continuous premelting dynamics in the transition regime toward polymer-like systems. By simulating alkane chains of varying lengths and analyzing temperature-dependent structural changes, we identify a crossover from discrete phase transitions to a gradual premelting process beyond chain lengths of N≈40 coarse-grained beads. The extrapolation of melting temperatures to zero heating rate yields values that agree well with the experimental data for the longest simulated chains. Compared to previous simulation studies, the slower heating rates used here offer enhanced quantitative agreement. Overall, the results provide new molecular-level insights into the melting of long-chain alkanes and highlight the utility of coarse-grained models in capturing complex phase behavior.