Reordering-mediated nucleation dynamics in early stage phase separation

Classical nucleation theories relying on quasi-equilibrium thermodynamics fail to capture the far-from-equilibrium structural reordering inherent to early stage condensed-cluster formation. We develop a framework that maps a continuous structural field onto a core-shell model, coupling local non-conservative reordering with mesoscopic phase-boundary propagation. By evaluating the reordering-mediated nucleation time, we analytically distinguish the static potential energy profile from the effective nucleation barrier. Our mean-field solution reveals a kinetic turnover effect: beyond a critical structural-density coupling threshold, rapid reordering dynamics induce a steep interfacial gradient in the structural field, incurring an energetic penalty that suppresses the net driving force for nucleation. This behavior highlights a fundamental non-reciprocity between cluster growth and local structural relaxation. The reordered intermediate states replicate experimentally observed size-dependent structural gradients and offer a resolution to discrepancies between classical predictions and measured nucleation rates, providing testable criteria for multi-step pathways in nanocrystallization and biomolecular condensation.

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Publication Details

Journal
The Journal of Chemical Physics
Published
2026-10-05
DOI
https://doi.org/10.1063/5.0352183
Primary Topic
nanoparticles nucleation surface interactions
Type
article
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article

Reordering-mediated nucleation dynamics in early stage phase separation

Haibin Su, Kaicheng Zhu
The Journal of Chemical Physics
nanoparticles nucleation surface interactions
article

Reordering-mediated nucleation dynamics in early stage phase separation

Haibin Su, Kaicheng Zhu
article en

Abstract

Classical nucleation theories relying on quasi-equilibrium thermodynamics fail to capture the far-from-equilibrium structural reordering inherent to early stage condensed-cluster formation. We develop a framework that maps a continuous structural field onto a core-shell model, coupling local non-conservative reordering with mesoscopic phase-boundary propagation. By evaluating the reordering-mediated nucleation time, we analytically distinguish the static potential energy profile from the effective nucleation barrier. Our mean-field solution reveals a kinetic turnover effect: beyond a critical structural-density coupling threshold, rapid reordering dynamics induce a steep interfacial gradient in the structural field, incurring an energetic penalty that suppresses the net driving force for nucleation. This behavior highlights a fundamental non-reciprocity between cluster growth and local structural relaxation. The reordered intermediate states replicate experimentally observed size-dependent structural gradients and offer a resolution to discrepancies between classical predictions and measured nucleation rates, providing testable criteria for multi-step pathways in nanocrystallization and biomolecular condensation.

The Journal of Chemical PhysicsVol. 165(13)
Hong Kong University of Science and Technology (HK), Hong Kong Jockey Club (HK), Institute for Advanced Study (DE), University of Hong Kong (HK)
Openalex Percentile: Top 17%
nanoparticles nucleation surface interactions
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