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首页> 外文期刊>Philosophical Magazine Letters >Double-well thermodynamic potentials and spinodal curves: how real are they?
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Double-well thermodynamic potentials and spinodal curves: how real are they?

机译：双井热力学势和旋节线曲线：它们有多真实？

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摘要

The concept of double-well thermodynamic potentials, ubiquitous since the van der Waals description of the vapour-to-liquid transition and the Landau theory of phase transitions, is critically re-examined. Particular emphasis is put on the extent to which spinodal curves (separating 'metastable' from 'unstable' states) are meaningful. It is argued that in full thermodynamic equilibrium spinodals are well-defined when one either considers finite subsystems of an infinitely large system, or systems with all linear dimensions finite. Evidence is given that in a finite (cubic) d-dimensional box the spinodals correspond (in a fluid) to the rounded 'droplet evaporation' or 'bubble condensation' transitions, respectively, and are shifted inside the bulk coexistence region by amounts of order L-d/(d+1), for a box of linear dimension L. The region in between the spinodals is the finite size analogue of the bulk two-phase coexistence region. Consequences for coarse-grained descriptions of the kinetics of phase transformations (e.g. cell dynamics simulations of spinodal decomposition, that start from a Ginzburg-Landau free energy functional) will be briefly discussed.
机译：自从范德华（Van der Waals）描述了气液转变和朗道（Landau）相变理论以来，普遍存在着双井热力学势的概念。特别强调的是旋节线曲线（将“可转移”与“不稳定”状态分开）在多大程度上有意义。有人认为，当人们考虑无限大系统的有限子系统或所有线性尺寸有限的系统时，在充分的热力学平衡旋节线中定义明确。有证据表明，在有限的（立体）d维框中，旋节线分别（在流体中）对应于圆形的“液滴蒸发”或“气泡凝结”过渡，并在整体共存区域内移位了数量级。对于线性尺寸为L的盒子，为Ld /（d + 1）。在旋节线之间的区域是本体两相共存区域的有限尺寸类似物。将简要讨论对相变动力学进行粗粒度描述的后果（例如，从Ginzburg-Landau自由能函数开始的旋节线分解的细胞动力学模拟）。

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