Equipartition and the temperature of maximum density of TIP4/2005 water

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Main Authors: Asthagiri, Dilipkumar N., Santos, Thiago Pinheiro dos, Beck, Thomas L.
Format: Preprint
Published: 2025
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author Asthagiri, Dilipkumar N.
Santos, Thiago Pinheiro dos
Beck, Thomas L.
author_facet Asthagiri, Dilipkumar N.
Santos, Thiago Pinheiro dos
Beck, Thomas L.
contents We simulate TIP4P/2005 water in the temperature range of 257 K to 318 K with time-steps $δ=$ 0.25, 0.50, 2.00, and 4.00 fs. The density-temperature behavior obtained using 0.25 or 0.50 fs are in excellent agreement with each other but differ from those obtained using time-steps that have been shown earlier to lead to a breakdown of equipartition. The temperature of maximum density (TMD) is 277.15 K with $δt = 0.25\;\mathrm{or}\; 0.50$ fs, but is shifted to progressively lower values for longer time-steps, a trend that holds for different thermostat/barostat combinations. Enhancing the water-water dispersion interaction, as has been recommended for simulating disordered proteins in TIP4P/2005, degrades the description of the liquid-vapor phase envelope. A key takeaway from this study is that using sufficiently short time-steps ($\leq 0.5$ fs) to preserve equipartition is essential for obtaining meaningful liquid water properties and for producing reliable data to parametrize biomolecular simulation models, as correct-ensemble sampling is fundamental to ensure reproducibility across codes and simulation alogrithms.
format Preprint
id arxiv_https___arxiv_org_abs_2508_14800
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Equipartition and the temperature of maximum density of TIP4/2005 water
Asthagiri, Dilipkumar N.
Santos, Thiago Pinheiro dos
Beck, Thomas L.
Soft Condensed Matter
Chemical Physics
We simulate TIP4P/2005 water in the temperature range of 257 K to 318 K with time-steps $δ=$ 0.25, 0.50, 2.00, and 4.00 fs. The density-temperature behavior obtained using 0.25 or 0.50 fs are in excellent agreement with each other but differ from those obtained using time-steps that have been shown earlier to lead to a breakdown of equipartition. The temperature of maximum density (TMD) is 277.15 K with $δt = 0.25\;\mathrm{or}\; 0.50$ fs, but is shifted to progressively lower values for longer time-steps, a trend that holds for different thermostat/barostat combinations. Enhancing the water-water dispersion interaction, as has been recommended for simulating disordered proteins in TIP4P/2005, degrades the description of the liquid-vapor phase envelope. A key takeaway from this study is that using sufficiently short time-steps ($\leq 0.5$ fs) to preserve equipartition is essential for obtaining meaningful liquid water properties and for producing reliable data to parametrize biomolecular simulation models, as correct-ensemble sampling is fundamental to ensure reproducibility across codes and simulation alogrithms.
title Equipartition and the temperature of maximum density of TIP4/2005 water
topic Soft Condensed Matter
Chemical Physics
url https://arxiv.org/abs/2508.14800