Accurate prediction of alkane phase transitions involving solids
is needed to prevent catastrophic pipeline blockages, improve lubrication
formulations, smart insulation, and energy storage, as well as bring
fundamental understanding to processes such as artificial morphogenesis.
However, simulation of these transitions is challenging and therefore
often omitted in force field development. Here, we perform a series
of benchmarks on seven representative molecular dynamics models (TraPPE,
PYS, CHARMM36, L-OPLS, COMPASS, Williams, and the newly optimized
Williams 7B), comparing with experimental data for liquid properties,
liquid–solid, and solid–solid phase transitions of two
prototypical alkanes, n-pentadecane (C15) and n-hexadecane (C16). We find that
existing models overestimate the melting points by up to 34 K, with
PYS and Williams 7B yielding the most accurate results deviating only
2 and 3 K from the experiment. We specially design order parameters
to identify crystal–rotator phase transitions in alkanes. United-atom
models could only produce a rotator phase with complete rotational
disorder, whereas all-atom models using a 12-6 Lennard-Jones potential
show no rotator phase even when superheated above the melting point.
In contrast, Williams (Buckingham potential) and COMPASS (9-6 Lennard-Jones)
reproduce the crystal-to-rotator phase transition, with the optimized
Williams 7B model having the most accurate crystal–rotator
transition temperature of C15.