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首页> 外文期刊>The Journal of Chemical Physics >Temporal cross-correlation asymmetry and departure from equilibrium in a bistable chemical system
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Temporal cross-correlation asymmetry and departure from equilibrium in a bistable chemical system

机译:双稳态化学系统中的时间互相关不对称和偏离平衡

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This paper aims at determining sustained reaction fluxes in a nonlinear chemical system driven in a nonequilibrium steady state. The method relies on the computation of cross-correlation functions for the internal fluctuations of chemical species concentrations. By employing Langevin-type equations, we derive approximate analytical formulas for the cross-correlation functions associated with nonlinear dynamics. Kinetic Monte Carlo simulations of the chemical master equation are performed in order to check the validity of the Langevin equations for a bistable chemical system. The two approaches are found in excellent agreement, except for critical parameter values where the bifurcation between monostability and bistability occurs. From the theoretical point of view, the results imply that the behavior of cross-correlation functions cannot be exploited to measure sustained reaction fluxes in a specific nonlinear system without the prior knowledge of the associated chemical mechanism and the rate constants. (C) 2014 AIP Publishing LLC.
机译:本文旨在确定在非平衡稳态下驱动的非线性化学系统中的持续反应通量。该方法依赖于化学物质浓度内部波动的互相关函数的计算。通过使用Langevin型方程,我们推导了与非线性动力学相关的互相关函数的近似解析公式。执行化学主方程的动力学蒙特卡洛模拟,以检查双稳态化学系统的Langevin方程的有效性。两种方法非常吻合,除了关键参数值外,在其中存在单稳性和双稳性之间的分歧。从理论的角度来看,结果暗示,如果没有相关化学机理和速率常数的先验知识,则不能利用互相关函数的行为来测量特定非线性系统中的持续反应通量。 (C)2014 AIP Publishing LLC。

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