Department of Chemical Science, University of Padova, Via Marzolo 1, 35131 Padova, Italy.
J Chem Phys. 2010 Jul 21;133(3):034510. doi: 10.1063/1.3456000.
A system composed of identical spins and described by a quantum mechanical pure state is analyzed within the statistical framework presented in Part I of this work. We explicitly derive the typical values of the entropy, of the energy, and of the equilibrium reduced density matrix of a subsystem for the two different statistics introduced in Part I. In order to analyze their consistency with thermodynamics, these quantities of interest are evaluated in the limit of large number of components of the isolated system. The main results can be summarized as follows: typical values of the entropy and of the equilibrium reduced density matrix as functions of the internal energy in the fixed expectation energy ensemble do not satisfy the requirement of thermodynamics. On the contrary, the thermodynamical description is recovered from the random pure state ensemble (RPSE), provided that one considers systems large enough. The thermodynamic limit of the considered properties for the spin system reveals a number of important features. First canonical statistics (and thus, canonical typicality as long as the fluctuations around the average value are small) emerges without the need of assuming the microcanonical space for the global pure state. Moreover, we rigorously prove (i) the equivalence of the "global temperature," derived from the entropy equation of state, with the "local temperature" determining the canonical state of the subsystems; and (ii) the equivalence between the RPSE typical entropy and the canonical entropy for the overall system.
在本工作第一部分中提出的统计框架内分析了由相同自旋组成且由量子力学纯态描述的系统。我们明确地推导出了在第一部分中引入的两种不同统计中,子系统的熵、能量和平衡约化密度矩阵的典型值。为了分析它们与热力学的一致性,在隔离系统的大量组成部分的极限下评估了这些感兴趣的量。主要结果可以概括如下:作为固定期望能量系综中内能函数的熵和平衡约化密度矩阵的典型值,不满足热力学的要求。相反,从随机纯态系综(RPSE)中恢复了热力学描述,前提是考虑足够大的系统。所考虑的自旋系统的性质的热力学极限揭示了许多重要的特征。首先,无需假设全局纯态的微正则空间,就可以出现正则统计(以及只要平均值周围的涨落较小,就可以出现正则典型性)。此外,我们严格证明了:(i)从状态熵方程得出的“全局温度”与确定子系统正则态的“局部温度”之间的等价性;以及(ii)整体系统的 RPSE 典型熵与正则熵之间的等价性。