热力学第五章热力学第二定律.pptVIP

非平衡统计理论的新进展 平衡态最大功原理：对于等温过程，系统对外做功小于（不可逆过程），或等于（可逆过程）自由能变化量的负数。 或 由于上不等式是一个统计定律，对于一个测量过程： 涨落—耗散定理 (Callen and Welton, 1951) 在近热力学平衡态的一个范围内： 反复测量系统对外界做功可以得到系统的状态函数增量。 Jarzynski’s Equality （1997） 从 Jarzynski’s Equality 推导涨落—耗散定理： 设测量的 值满足类高斯分布, 对等式左边作关于 的泰劳展开： Crooks’ Law: Entropy production fluctuation theorem A generalized version of the fluctuation theorem for stochastic, microscopically reversible dynamics. w: the entropy production of the driven system measured over some time interval; PF(ω): the probability of finding this entropy production in the repeat experiments; PR(ω): the probability of finding the entropy production in the same experiments. Example The microscopic dynamics of the system will differ for each repetition of this process, as will the entropy production, the heat transfer, and the work performed on the system. The probability distribution is measured over the ensemble of repetitions. The Crooks’s law gives a probability of particular paths measured by entropy production. Contain more information than Jarzynski’ equality. Since we can deduce it from Crooks’ law. Meaning Crooks’ law: Entropy production: Jarzynski equality Applicable to all the microscopically reversible process; Applicable in all kinds of baths. (isothermal-isobaric). Hatano and Sasa’s equilibrium steady state equality Quantitatively measure the probability of break the second principle of thermodynamics. Portion that Against 2ed law The measurable of deviation can only be observable when the dissipation is small. Test Trivial case: if has a Gaussian distribution, one has: With the system obeys fluctuation-dissipation law, one get Crook’s law. Experiment I Drag a microscopic bead through water by using a storable harmonic optical trap. The entropy production can be derived to be The negative entropy production (-Y) in all three experiments are equal to one, confirming the strongest prediction of Hatano and Sasa. Experiment II Crooks’ law provides