Saved in:
Bibliographic Details
Main Authors: Jiang, Xinyue, Shang, Yating, Li, Jianhui, Zou, Zhaoyong, Zuo, Yanxia, Xie, Yuqun
Format: Preprint
Published: 2026
Subjects:
Online Access:https://arxiv.org/abs/2605.25457
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1866913161250078720
author Jiang, Xinyue
Shang, Yating
Li, Jianhui
Zou, Zhaoyong
Zuo, Yanxia
Xie, Yuqun
author_facet Jiang, Xinyue
Shang, Yating
Li, Jianhui
Zou, Zhaoyong
Zuo, Yanxia
Xie, Yuqun
contents Ethanol-water mixtures are a classic example of thermodynamic non-ideality, yet the structural origin of their pronounced anomalies, such as volume contraction and a large negative excess entropy, has remained a long-standing puzzle. Here, we demonstrate these anomalies are not equilibrium properties but calorimetric fingerprint of an arrested phase transition. By imposing periodic thermal oscillations, we drive a 50% (v/v) ethanol-water system along a complete hierarchical self-assembly pathway that progressed from ethanol clusters to water-containing droplets, then to acicular flakes, and finally to micron-scale ordered ethanol aggregates. Fluorescence spectroscopy, two-dimensional correlation analysis and nuclear magnetic resonance revealed the underlying non-equilibrium molecular mechanism: a periodic perturbation of the water-dominated hydrogen-bond network initiates a ethanol-water coexistence intermediate, ultimately leading to the stable ordered assembly of an ethanol-rich phase. Our finding demonstrated that periodic physical perturbations capable drive spontaneous ordering across multiple length scales in a simple binary mixture, providing a kinetic perspective on the structural origin of solution non-ideality, and carry general implications for self-assembly strategies in soft matter.
format Preprint
id arxiv_https___arxiv_org_abs_2605_25457
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Non-equilibrium pathway to mesoscale ordering in ethanol-water binary liquid
Jiang, Xinyue
Shang, Yating
Li, Jianhui
Zou, Zhaoyong
Zuo, Yanxia
Xie, Yuqun
Soft Condensed Matter
Atomic Physics
Ethanol-water mixtures are a classic example of thermodynamic non-ideality, yet the structural origin of their pronounced anomalies, such as volume contraction and a large negative excess entropy, has remained a long-standing puzzle. Here, we demonstrate these anomalies are not equilibrium properties but calorimetric fingerprint of an arrested phase transition. By imposing periodic thermal oscillations, we drive a 50% (v/v) ethanol-water system along a complete hierarchical self-assembly pathway that progressed from ethanol clusters to water-containing droplets, then to acicular flakes, and finally to micron-scale ordered ethanol aggregates. Fluorescence spectroscopy, two-dimensional correlation analysis and nuclear magnetic resonance revealed the underlying non-equilibrium molecular mechanism: a periodic perturbation of the water-dominated hydrogen-bond network initiates a ethanol-water coexistence intermediate, ultimately leading to the stable ordered assembly of an ethanol-rich phase. Our finding demonstrated that periodic physical perturbations capable drive spontaneous ordering across multiple length scales in a simple binary mixture, providing a kinetic perspective on the structural origin of solution non-ideality, and carry general implications for self-assembly strategies in soft matter.
title Non-equilibrium pathway to mesoscale ordering in ethanol-water binary liquid
topic Soft Condensed Matter
Atomic Physics
url https://arxiv.org/abs/2605.25457