Importance of nuclear quantum effects on the structure of supercooled water around its liquid--liquid critical point

Fuente: arXiv
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Main Authors: Beerbaum, Michael, Heske, Julian, Gujt, Jure, Kühne, Thomas D.
Format: Preprint
Published: 2026
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_version_ 1866909055272878080
author Beerbaum, Michael
Heske, Julian
Gujt, Jure
Kühne, Thomas D.
author_facet Beerbaum, Michael
Heske, Julian
Gujt, Jure
Kühne, Thomas D.
contents Supercooled water is expected to exhibit a liquid--liquid phase transition between low- and high-density liquid states, possibly terminating in a liquid--liquid critical point in the experimentally difficult no man's land. Because the hydrogen atoms are light, nuclear quantum effects (NQE) may alter the structural signatures used to identify this transition. Here, we compare classical molecular dynamics and path-integral molecular dynamics simulations of a flexible q-TIP4P/F-like water model in the deeply supercooled regime. The classical simulations show a pronounced density change at 180 K between 180 and 220 MPa, whereas the path-integral simulations exhibit a smoother pressure dependence. Radial distribution functions and bond-order parameters show that NQE broaden pair correlations, reduce the tetrahedral order of the first hydration shell, and slightly increase the Steinhardt $Q_6$ parameter. These results demonstrate that NQE modify both low- and high-density liquid structures and therefore need to be included when interpreting structural signatures of the liquid--liquid transition in supercooled water.
format Preprint
id arxiv_https___arxiv_org_abs_2605_19175
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Importance of nuclear quantum effects on the structure of supercooled water around its liquid--liquid critical point
Beerbaum, Michael
Heske, Julian
Gujt, Jure
Kühne, Thomas D.
Chemical Physics
Disordered Systems and Neural Networks
Soft Condensed Matter
Statistical Mechanics
Computational Physics
Supercooled water is expected to exhibit a liquid--liquid phase transition between low- and high-density liquid states, possibly terminating in a liquid--liquid critical point in the experimentally difficult no man's land. Because the hydrogen atoms are light, nuclear quantum effects (NQE) may alter the structural signatures used to identify this transition. Here, we compare classical molecular dynamics and path-integral molecular dynamics simulations of a flexible q-TIP4P/F-like water model in the deeply supercooled regime. The classical simulations show a pronounced density change at 180 K between 180 and 220 MPa, whereas the path-integral simulations exhibit a smoother pressure dependence. Radial distribution functions and bond-order parameters show that NQE broaden pair correlations, reduce the tetrahedral order of the first hydration shell, and slightly increase the Steinhardt $Q_6$ parameter. These results demonstrate that NQE modify both low- and high-density liquid structures and therefore need to be included when interpreting structural signatures of the liquid--liquid transition in supercooled water.
title Importance of nuclear quantum effects on the structure of supercooled water around its liquid--liquid critical point
topic Chemical Physics
Disordered Systems and Neural Networks
Soft Condensed Matter
Statistical Mechanics
Computational Physics
url https://arxiv.org/abs/2605.19175