受高斯白噪声影响的有限化学反应体系的随机热力学——外噪声对化学反应体系影响的有效热力学量度

通过分析噪声对跃迁概率的不同影响,借助Novikov定理及MSR理论,建立了受多源白噪声影响的有限化学反应体系的有效主方程及有效熵平衡方程,导出非平衡定态时这类噪声体系熵产生的一般表达式,揭示涨落熵产生的统计内涵及噪声贡献,并针对非宏观量级的外噪声,借助扰动按分布参数分离法及有效主方程的Kramers-Moyal展开,进一步对简单加合性噪声建立了非平衡定态宏观稳定性判据的随机模拟,论证了噪声对化学反应体系定态稳定性的弱化作用.     

非平衡定态化学反应体系对细致平衡偏离的不可逆性之随机热力学量度

在随机描述的层次上,成功地构筑了非平衡定态化学反应体系对细致平衡偏离的不可逆性之随机热力学判据.基于Fokker-Planck方程建立了连续Markov过程系统的随机熵平衡方程,发现在随机态空间中随机熵的时间变率亦可分为源项和流项两部分贡献.对于化学反应体系,作为态空间源项的随机熵产生可作为偏离细致平衡不可逆性的合适度量,此泛函量的零值标志着细致平衡.进一步借助按系统广度量的Ω展开法,通过对随机力及共轭的随机流的分析揭示态空间中的随机熵产生仅源于状态对细致平衡的偏离,并主要来自非Poisson涨落的贡献,因而可作为随机热力学量去判别和量度化学反应体系对细致平衡的偏离.     

"信息"到底是什么?--限于无生命、物质和科学领域的讨论

本文在无生命、物质和科学三个限制的前提下讨论“信息”到底是什么.依次论证：（1）自然科学没有能力度量信息的“质”,只能讨论信息的“量”;（2）“信息熵”只是度量信息“量”的概念;（3）在无生命的物质科学领域内,信息熵完全等价于Boltzmann熵,对应于实验中的热熵;（4）运用Occam剃刀原理,信息熵和Boltzmann熵两个名词只能留下其中的任意一个;（5）“熵”取决于体系的微观状态总数,即最终取决于热运动引起的分子核骨架的动态变化.于是,在无生命、物质和科学三个限制的领域内“信息”只是望文生义的产物.     

Brusselator的化学亲合势及熵产生的振荡

迄今为止,化学振荡的研究主要限于描述物质浓度的振荡,有关热力学量的振荡报导极少.这可能是由于振荡机理(或模型)中的热力学量无法确定的缘故.我们采用将标准化学亲合势作为可调参数的方法,并依据非平衡态热力学理论中热力学量与物质的浓度关系,使得热力学量振荡的研究变为现实.本文用计算机数值计算,得出了开放系Brusseltor各元反应的反应速率、化学亲合势及体系熵产生随时间的变化行为,展示了它们的振荡特征。     

气液色谱法研究C8芳烃在N-(对乙氧基苄叉)对氨基苯甲腈液晶中的溶液热力学: 液晶的相变

在不同温度下测量了C8芳烃在N-(对乙氧基苄叉)对氨基苯甲腈向列相及各向同性相中的活度系数、过量偏摩尔焓及过量偏摩尔熵. 引入无因次量σ和τ以处理实验数据,发现所研究的体系, 处于相同的τ下, 近似具有相同的σ.     

PMMI/PVDF共混体系相分离的时温依赖性

用小角激光光散射(SALLS)研究了聚(N-甲基甲基丙烯酰亚胺)/聚偏氟乙烯(PMMI/PVDF)共混体系的相分离行为.通过升温法获得了PMMI/PVDF体系的浊点温度,发现体系的浊点温度强烈依赖于升温速率,呈明显的非线性关系,即升温速率大于1 K.min-1时,升温速率是影响I(t)的唯一因素;升温速率较小时,高分子链松弛速率的差别得以体现,则该情况下升温速率与松弛速率共同影响浊点温度.该体系具有典型的最低临界共溶温度(LCST)特征.恒温法相分离结果表明,在实验温度范围内该体系相分离行为对温度的依赖性遵循时温叠加(time-temperature superposition,TTS)原理.     

关于能量最低原理的误读——论“凭什么相信计算”之二

不要把能量最低原理与核外电子填充规则混为一谈,后者仅仅是能量最低原理众多应用中的一例。体系"能量越低越稳定"的说法错在忘了它成立的前提:熵固定。Gibbs的说法才是能量最低原理的完整表述,它等价于Clausius的最大熵原理,两者各自有其成立的前提条件。由Gibbs能量最低原理可以导出核外电子的填充规则。宏观和微观世界只有一个能量最低原理。     

强熵效应与大分子体系的熵调控

在大分子体系中,以链的构象熵为主的熵效应对体系的微观结构和宏观性能都起着至关重要的作用.然而,熵的统计本质使其远不像焓作用那么直观,甚至会导致反直觉的现象出现.因此,探寻大分子体系中的熵效应,对于深入揭示此类体系纷繁复杂现象背后物理机制的重要性来说是不言而喻的,已成为高分子与软凝聚态物理学以及生命科学等多学科相交叉的重要前沿研究领域.如何在阐释熵效应的独特作用规律基础上,有效地调控熵以实现对体系微观结构的熵调控进而发展新型功能体系,是该领域一个亟需解决的重要科学问题.本文总结了我们在提出并发展熵调控策略方面的研究进展.首先,剖析了熵效应的一些基本作用规律,涵盖熵致有序和熵力等,并进一步提出了强熵效应的概念.其次,阐述了熵调控策略的必要性、基本原理以及调控途径.同时,举例介绍了熵调控策略在大分子体系中的应用,涵盖高分子纳米复合体系、凝胶网络、生命大分子体系以及大分子胶体体系等.最后,简明扼要地展望了该领域的未来发展趋势以及面临的关键问题,以期为其以后的发展提供些许有益的启迪.     

气液色谱法研究C8芳烃在N-(对乙氧基苄叉)对氨基苯甲腈液晶中的溶液热力学: 液晶的相变

在不同温度下测量了C_8芳烃在N-(对乙氧基苄叉)对氨基苯甲腈向列相及各向同性相中的活度系数、过量偏摩尔焓及过量偏摩尔熵。引入无因次量σ和τ以处理实验数据,发现所研究的体系,处于相同的τ下,近似具有相同的σ。     

立方体纳米氧化亚铜反应动力学的理论及实验研究

为了探究纳米多相反应过程的动力学行为,本文通过液相还原法可控合成了粒度为55 nm的立方体氧化亚铜（Cu₂O）。基于纳米与块体Cu₂O的区别,采用原位微量热技术获取Cu₂O体系与HNO₃反应过程的热动力学精细信息,结合热动力学原理及动力学过渡态理论计算得到Cu₂O反应动力学参数,并建立立方体动力学模型讨论并佐证动力学实验结果。结果表明,纳米Cu₂O的反应速率常数大于块体,而表观活化能、指前因子、活化焓、活化熵和活化Gibbs自由能均小于块体;随着温度的升高,纳米Cu₂O的反应速率常数和活化Gibbs自由能均增大。动力学模型表明影响反应动力学参数的主要因素为：偏摩尔表面焓影响表观活化能,偏摩尔表面熵影响指前因子,偏摩尔表面Gibbs自由能影响反应速率常数。本文为纳米材料多相反应动力学参数的获取和分析应用提供了一种普适的理论模型和实验方法。     

A Stochastic Extension of Macroscopic Stability Criterion of Nonequilibrium Steady State in Chemical Reaction Systems Governed by Master Equation

By means of both the separation of the perturbation in accordance with characteristic parnmeters and the Kramers Moyal-expansion of the master equation, it is shown that the time derivative of the partial excess quantity of stochastic entropy due to the deviation from the most probable path is related to the responsibility of a system to the external macroscopic perturbations. This evolution rate of the partial excess stochastic entropy is equivalent to the partlal excess stochastic entropy production, as well as the stochastic excess entropy production rate based on the stochastic potential npproach. It appears also as an eqivalent quantity of the Gibbs excess entropy production for the Polsson distribution. The macroscopic stability of chemical reaction systems is dominnted by this new stochastic quantity when the local equilibrium thermodynamics is broken down .     

Entropic estimate of cooperative binding of substrate on a single oligomeric enzyme: an index of cooperativity

Here we have systematically studied the cooperative binding of substrate molecules on the active sites of a single oligomeric enzyme in a chemiostatic condition. The average number of bound substrate and the net velocity of the enzyme catalyzed reaction are studied by the formulation of stochastic master equation for the cooperative binding classified here as spatial and temporal. We have estimated the entropy production for the cooperative binding schemes based on single trajectory analysis using a kinetic Monte Carlo technique. It is found that the total as well as the medium entropy production shows the same generic diagnostic signature for detecting the cooperativity, usually characterized in terms of the net velocity of the reaction. This feature is also found to be valid for the total entropy production rate at the non-equilibrium steady state. We have introduced an index of cooperativity, C, defined in terms of the ratio of the surprisals or equivalently, the stochastic system entropy associated with the fully bound state of the cooperative and non-cooperative cases. The criteria of cooperativity in terms of C is compared with that of the Hill coefficient of some relevant experimental result and gives a microscopic insight on the mechanism of cooperative binding of substrate on a single oligomeric enzyme which is usually estimated from the macroscopic reaction rate.     

Entropy production of a mechanically driven single oligomeric enzyme: a consequence of fluctuation theorem

In this work we have shown how an applied mechanical force affects an oligomeric enzyme kinetics in a chemiostatic condition where the statistical characteristics of random walk of the substrate molecules over a finite number of active sites of the enzyme plays important contributing factors in governing the overall rate and nonequilibrium thermodynamic properties. The analytical results are supported by the simulation of single trajectory based approach of entropy production using Gillespie’s stochastic algorithm. This microscopic numerical approach not only gives the macroscopic entropy production from the mean of the distribution of entropy production which depends on the force but also a broadening of the distribution by the applied mechanical force, a kind of power broadening. In the nonequilibrium steady state (NESS), both the mean and the variance of the distribution increases and then saturates with the rise in applied force corresponding to the situation when the net rate of product formation reaches a limiting value with an activationless transition. The effect of the system-size and force on the entropy production distribution is shown to be constrained by the detailed fluctuation theorem.     

A thermodynamic approach to the fragility of glass-forming polymers

We have connected the dynamic fragility, namely, the steepness of the relaxation-time variation upon temperature reduction, to the excess entropy and heat capacity of a large number of glass-forming polymers. The connection was obtained in a natural way from the Adam-Gibbs equation, relating the structural relaxation time to the configurational entropy. We find a clear correlation for a group of polymers. For another group of polymers, for which this correlation does not work, we emphasize the role of relaxation processes unrelated to the alpha process in affecting macroscopic thermodynamic properties. Once the residual excess entropy at the Vogel temperature is removed from the total excess entropy, the correlation between dynamic fragility and thermodynamic properties is reestablished.     

溶剂化的热力学集团展开理论

把二元溶液的过剩内能（excess energy）分成溶剂-溶剂、溶剂-溶质及溶质-溶质相互作用部分。利用集团展开方法给出了二元溶液在正则系综的配分函数的表达式,利用该表达式得到了溶质的偏摩尔内能(partial molar energy)和偏摩尔熵(partial molar entropy)的表达式。在无限稀溶液情形,过剩偏摩尔内能的溶剂-溶剂部分又称重组织内能（reorganization energy）,它反映了溶质存在时对其周围溶剂分子之间的相互作用能的影响。研究表明,在溶质的粒子数密度相对较大时,溶质分子之间的相互作用将影响过剩偏摩尔内能的溶剂-溶剂部分,对于稀溶液,过剩偏摩尔内能的溶剂-溶剂部分与溶质的摩尔分数成线性关系。对低密度二元溶液,溶质的过剩偏摩尔内能和过剩偏摩尔熵也与溶质的摩尔分数成线性关系。     

Fluctuation theorem for nonequilibrium reactions

A fluctuation theorem is derived for stochastic nonequilibrium reactions ruled by the chemical master equation. The theorem is expressed in terms of the generating and large-deviation functions characterizing the fluctuations of a quantity which measures the loss of detailed balance out of thermodynamic equilibrium. The relationship to entropy production is established and discussed. The fluctuation theorem is verified in the Schl?gl model of far-from-equilibrium bistability.     

Confinement, entropy, and single-particle dynamics of equilibrium hard-sphere mixtures

We use discontinuous molecular dynamics and grand-canonical transition-matrix Monte Carlo simulations to explore how confinement between parallel hard walls modifies the relationships between packing fraction, self-diffusivity, partial molar excess entropy, and total excess entropy for binary hard-sphere mixtures. To accomplish this, we introduce an efficient algorithm to calculate partial molar excess entropies from the transition-matrix Monte Carlo simulation data. We find that the species-dependent self-diffusivities of confined fluids are very similar to those of the bulk mixture if compared at the same, appropriately defined, packing fraction up to intermediate values, but then deviate negatively from the bulk behavior at higher packing fractions. On the other hand, the relationships between self-diffusivity and partial molar excess entropy (or total excess entropy) observed in the bulk fluid are preserved under confinement even at relatively high packing fractions and for different mixture compositions. This suggests that the excess entropy, calculable from classical density functional theories of inhomogeneous fluids, can be used to predict some of the nontrivial dynamical behaviors of fluid mixtures in confined environments.