Popov Alexander V, Hernandez Rigoberto
Center for Computational and Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
J Chem Phys. 2007 Jun 28;126(24):244506. doi: 10.1063/1.2743032.
The laws of thermodynamics provide a clear concept of the temperature for an equilibrium system in the continuum limit. Meanwhile, the equipartition theorem allows one to make a connection between the ensemble average of the kinetic energy and the uniform temperature. When a system or its environment is far from equilibrium, however, such an association does not necessarily apply. In small systems, the regression hypothesis may not even apply. Herein, it is shown that in small nonequilibrium systems, the regression hypothesis still holds, though with a generalized definition of the temperature. The latter must now be defined for each such manifestation.
热力学定律为连续极限下的平衡系统提供了清晰的温度概念。同时,能量均分定理使人们能够在动能的系综平均值和均匀温度之间建立联系。然而,当一个系统或其环境远离平衡时,这种关联不一定适用。在小系统中,回归假设甚至可能不适用。在此表明,在小的非平衡系统中,回归假设仍然成立,尽管温度有了广义定义。现在必须为每个这样的表现形式定义后者。