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PreprintCC BY 4.0arXiv

An anharmonic liquid-entropy functional from the Mori-Zwanzig memory kernel

  • Ricardo Buarque
  • Mauro Gascon
  • Tod A. Pascal
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Abstract

We utilize the Mori-Zwanzig memory kernel to separate the density of states of a liquid into gas, cage, and harmonic-solid components. The cage entropy is computed self-consistently as the non-Markovian excess of the full velocity response over its Markovian counterpart, and is assigned an excluded-volume entropy reference rather than a harmonic one. Employing physically motivated constraints, the resulting Three-Phase Explicit Anharmonic Thermodynamics (3PT) method reproduces thermodynamic-integration entropies of liquid metals and aligns two water models with independent free-energy perturbation benchmarks. For monoatomic Lennard-Jones liquids, 3PT's accuracy follows a universal efficiency curve governed by the kernel's non-Markovianity. We thus establish a direct, trajectory-level mapping between memory, transient cage dynamics, and liquid entropy.

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Cite

BibTeXRIS
BibTeX
@misc{buarque2026anharmonic,
  title = {{An anharmonic liquid-entropy functional from the Mori-Zwanzig memory kernel}},
  author = {Ricardo Buarque and Mauro Gascon and Tod A. Pascal},
  howpublished = {arXiv},
  year = {2026},
  month = aug,
  doi = {10.48550/arxiv.2607.29026},
  eprint = {2607.29026},
  archivePrefix = {arXiv},
  url = {https://arxiv.org/abs/2607.29026},
  note = {CC BY 4.0},
}
RIS
TY  - UNPB
TI  - An anharmonic liquid-entropy functional from the Mori-Zwanzig memory kernel
AU  - Ricardo Buarque
AU  - Mauro Gascon
AU  - Tod A. Pascal
PY  - 2026
DA  - 2026/08/31
PB  - arXiv
DO  - 10.48550/arxiv.2607.29026
UR  - https://arxiv.org/abs/2607.29026
AB  - We utilize the Mori-Zwanzig memory kernel to separate the density of states of a liquid into gas, cage, and harmonic-solid components. The cage entropy is computed self-consistently as the non-Markovian excess of the full velocity response over its Markovian counterpart, and is assigned an excluded-volume entropy reference rather than a harmonic one. Employing physically motivated constraints, the resulting Three-Phase Explicit Anharmonic Thermodynamics (3PT) method reproduces thermodynamic-integration entropies of liquid metals and aligns two water models with independent free-energy perturbation benchmarks. For monoatomic Lennard-Jones liquids, 3PT's accuracy follows a universal efficiency curve governed by the kernel's non-Markovianity. We thus establish a direct, trajectory-level mapping between memory, transient cage dynamics, and liquid entropy.
ER  -