Comparison of all atom and united atom models for thermal transport calculations of amorphous polyethylene

TL;DR

This study compares all-atom and united atom models for calculating thermal transport in amorphous polyethylene, revealing that united atom models underestimate thermal conductivity due to softer interactions and missing degrees of freedom.

Contribution

It provides a systematic comparison showing that united atom models are less accurate for thermal transport predictions than all-atom models in amorphous polyethylene.

Findings

United atom models underestimate thermal conductivity compared to all-atom models.

UA models exhibit weaker mechanical response and softer interactions.

Bonded and nonbonded contributions to thermal conductivity are analyzed.

Abstract

Polymer simulations routinely employ models with different molecular resolutions. United atom (UA) models are one such example, where groups of certain atoms in a molecule are clustered into superatoms. Although their computational simplicity makes them particularly attractive for studying a wide range of polymer properties, the missing degrees of freedom in UA models can impact certain properties that are intimately linked to localized vibrations, such as the heat capacity and the thermal transport coefficient $\kappa$. In contrast, the numerically exhausting all atom (AA) models produce results that better match experimental data. In this work, we systematically investigate and compare $\kappa$ obtained from an AA and a UA models for an amorphous polyethylene system. The results indicate that the UA description may not be a suitable model for evaluating thermal transport, since it underestimates $\kappa$ in comparison to an AA description and the experimental value. The coarse-graining leads to the softer interactions and its presence is highlighted in a weaker mechanical response from the UA model, thus also underestimates $\kappa$. We further consolidate our findings by extracting the bonded and the nonbonded contributions to $\kappa$ within the framework of the single chain energy transfer model.