Comparing simulated specific heat of liquid polymers and oligomers to experiments

HY Gao and TPW Menzel and MH Muser and D Mukherji, PHYSICAL REVIEW MATERIALS, 5, 065605 (2021).

DOI: 10.1103/PhysRevMaterials.5.065605

Specific heat is a central property of condensed matter systems including polymers and oligomers in their condensed phases, yet predictions of this quantity from molecular simulations and successful comparisons with experimental data are scarce if existing at all. One reason for this may be that the internal energy and thus the specific heat cannot be coarse-grained so that they defy their rigorous computation with united-atom models. Moreover, many modes in a polymer barely contribute to the specific heat because of their quantum mechanical nature. Here, we demonstrate that an analysis of the mass- weighted velocity autocor-relation function allows specific heat predictions to be corrected for quantum effects so that agreement with experimental data is on par with predictions of other routinely computed quantities. We outline how to construct corrections for both all-atom and united-atom descriptions of chain molecules. Corrections computed for 11 hydrocarbon oligomers and commodity polymers deviate by

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