Projected free energies for polydisperse phase equilibria
Projected free energies for polydisperse phase equilibria
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DOI：
10.1103/physrevlett.80.1365
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发表时间：
1998-02-16
影响因子：
8.6
通讯作者：
Cates, ME
中科院分区：
文献类型：
--
作者：
Sollich, P;Cates, ME
一个“多分散”系统有无限多个守恒密度。我们给出了一个将其无限维自由能面投影到由有限个线性密度组合(“矩”)组成的子空间上的有理过程，然后照常找到了它的相行为。如果系统的过剩自由能只取决于所用的力矩，则会产生精确的云、阴影和旋节曲线；两相和多相区域是近似的，但通过添加额外的力矩可以无限细化。该方法在计算上是可靠的，并给出了对多分散热力学的新的几何见解。
A "polydisperse" system has an infinite number of conserved densities. We give a rational procedure for projecting its infinite-dimensional free energy surface onto a subspace comprising a finite number of linear combinations of densities ("moments"), in which the phase behavior is then found as usual. If the excess free energy of the system depends only on the moments used, exact cloud, shadow, and spinodal curves result; two-phase and multiphase regions are approximate, but refinable indefinitely by adding extra moments. The approach is computationally robust and gives new geometrical insights into the thermodynamics of polydispersity.