The Free-Energy Barrier of Precritical Nuclei in Hard Spheres is Consistent with Predictions

Fuente: arXiv
Saved in:
Bibliographic Details
Main Authors: Kürten, Lars, Castagnède, Antoine, Smallenburg, Frank, Royall, C. Patrick
Format: Preprint
Published: 2025
Subjects:
Online Access:
Tags: Add Tag
No Tags, Be the first to tag this record!
_version_ 1866912411603173376
author Kürten, Lars
Castagnède, Antoine
Smallenburg, Frank
Royall, C. Patrick
author_facet Kürten, Lars
Castagnède, Antoine
Smallenburg, Frank
Royall, C. Patrick
contents Predicting crystal nucleation is among the most significant long--standing challenges in condensed matter. In the system most studied (hard sphere colloids), the comparison between experiments performed using static light scattering and computer simulations is woeful, with a discrepancy of over 10 orders of magnitude. The situation with other well-studied materials (such as water and sodium chloride) is no better. It has thus far proven impossible to access the regime of this discrepancy with particle-resolved techniques which might shed light on its origins, due to the relatively sluggish dynamics of the larger colloids required for confocal microscopy. Here we address this challenge with two developments. Our work is a marked improvement in the precision of mapping the state point of experiments to simulation. For this, we employed a combination of novel machine-learning methods for particle tracking and higher-order correlation functions. Our second innovation is to consider the free energy of pre-critical nuclei which can be detected in the discrepancy regime. These are in agreement with computer simulation. This is the first time that such free energies have been successfully compared between experiment and simulation in any material as far as we are aware. The agreement provides important validation of rare event sampling techniques which are used very widely in simulation, but which can seldom be directly compared with experiment.
format Preprint
id arxiv_https___arxiv_org_abs_2503_17270
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle The Free-Energy Barrier of Precritical Nuclei in Hard Spheres is Consistent with Predictions
Kürten, Lars
Castagnède, Antoine
Smallenburg, Frank
Royall, C. Patrick
Soft Condensed Matter
Statistical Mechanics
Predicting crystal nucleation is among the most significant long--standing challenges in condensed matter. In the system most studied (hard sphere colloids), the comparison between experiments performed using static light scattering and computer simulations is woeful, with a discrepancy of over 10 orders of magnitude. The situation with other well-studied materials (such as water and sodium chloride) is no better. It has thus far proven impossible to access the regime of this discrepancy with particle-resolved techniques which might shed light on its origins, due to the relatively sluggish dynamics of the larger colloids required for confocal microscopy. Here we address this challenge with two developments. Our work is a marked improvement in the precision of mapping the state point of experiments to simulation. For this, we employed a combination of novel machine-learning methods for particle tracking and higher-order correlation functions. Our second innovation is to consider the free energy of pre-critical nuclei which can be detected in the discrepancy regime. These are in agreement with computer simulation. This is the first time that such free energies have been successfully compared between experiment and simulation in any material as far as we are aware. The agreement provides important validation of rare event sampling techniques which are used very widely in simulation, but which can seldom be directly compared with experiment.
title The Free-Energy Barrier of Precritical Nuclei in Hard Spheres is Consistent with Predictions
topic Soft Condensed Matter
Statistical Mechanics
url https://arxiv.org/abs/2503.17270