Laboratoire Charles Fabry, UMR 8501, Institut d'Optique, CNRS, Université Paris-Saclay, 2 Avenue Augustin Fresnel, 91127 Palaiseau Cedex, France.
Departament de Física de la Matèria Condensada, Facultat de Física, Universitat de Barcelona, Martí i Franquès 1, 08028 Barcelona, Spain.
Phys Rev E. 2017 Jan;95(1-1):012140. doi: 10.1103/PhysRevE.95.012140. Epub 2017 Jan 23.
Completely open systems can exchange heat, work, and matter with the environment. While energy, volume, and number of particles fluctuate under completely open conditions, the equilibrium states of the system, if they exist, can be specified using the temperature, pressure, and chemical potential as control parameters. The unconstrained ensemble is the statistical ensemble describing completely open systems and the replica energy is the appropriate free energy for these control parameters from which the thermodynamics must be derived. It turns out that macroscopic systems with short-range interactions cannot attain equilibrium configurations in the unconstrained ensemble, since temperature, pressure, and chemical potential cannot be taken as a set of independent variables in this case. In contrast, we show that systems with long-range interactions can reach states of thermodynamic equilibrium in the unconstrained ensemble. To illustrate this fact, we consider a modification of the Thirring model and compare the unconstrained ensemble with the canonical and grand-canonical ones: The more the ensemble is constrained by fixing the volume or number of particles, the larger the space of parameters defining the equilibrium configurations.
完全开放的系统可以与环境进行热交换、功交换和物质交换。在完全开放的条件下,能量、体积和粒子数会发生波动,但如果存在平衡状态,可以使用温度、压力和化学势作为控制参数来指定系统的平衡状态。无约束系综是描述完全开放系统的统计系综,副本能量是这些控制参数的适当自由能,必须从这些控制参数中推导出热力学。事实证明,具有短程相互作用的宏观系统不能在无约束系综中达到平衡构型,因为在这种情况下,温度、压力和化学势不能作为一组独立变量。相比之下,我们表明具有长程相互作用的系统可以在无约束系综中达到热力学平衡状态。为了说明这一事实,我们考虑了 Thirring 模型的一种修改,并比较了无约束系综与正则系综和巨正则系综:通过固定体积或粒子数来约束系综的程度越大,定义平衡构型的参数空间就越大。