Carberry D M, Reid J C, Wang G M, Sevick E M, Searles Debra J, Evans Denis J
Research School of Chemistry, The Australian National University, Canberra ACT 0200 Australia.
Phys Rev Lett. 2004 Apr 9;92(14):140601. doi: 10.1103/PhysRevLett.92.140601. Epub 2004 Apr 6.
The puzzle of how time-reversible microscopic equations of mechanics lead to the time-irreversible macroscopic equations of thermodynamics has been a paradox since the days of Boltzmann. Boltzmann simply sidestepped this enigma by stating "as soon as one looks at bodies of such small dimension that they contain only very few molecules, the validity of this theorem [the second law of thermodynamics and its description of irreversibility] must cease." Today we can state that the transient fluctuation theorem (TFT) of Evans and Searles is a generalized, second-law-like theorem that bridges the microscopic and macroscopic domains and links the time-reversible and irreversible descriptions. We apply this theorem to a colloidal particle in an optical trap. For the first time, we demonstrate the TFT in an experiment and show quantitative agreement with Langevin dynamics.
自玻尔兹曼时代以来,时间可逆的微观力学方程如何导致时间不可逆的宏观热力学方程这一难题一直是个悖论。玻尔兹曼只是简单地回避了这个谜团,他指出:“一旦观察尺寸如此之小以至于只包含极少数分子的物体,这个定理[热力学第二定律及其对不可逆性的描述]的有效性必然不再成立。”如今我们可以说,埃文斯和西尔斯的瞬态涨落定理(TFT)是一个广义的、类似第二定律的定理,它架起了微观和宏观领域之间的桥梁,并将时间可逆和不可逆描述联系起来。我们将这个定理应用于光学阱中的胶体粒子。我们首次在实验中证明了TFT,并显示出与朗之万动力学的定量一致性。