用随机马库斯状态模型阐明非平衡多步反应动态.
1Department of Chemistry, The Hong Kong University of Science and Technology, Kowloon, Hong Kong.
The Journal of chemical physics
|November 20, 2025
概括
这项研究引入了一个新的随机马库斯状态模型来分析复杂的,多步骤的化学反应. 该模型澄清了随机反应动力学,并将马库斯理论扩展到连续的化学状态空间.
科学领域:
- 化学物理 化学物理
- 统计力学 统计力学
- 理论化学 理论化学
背景情况:
- 随机反应动力学对于理解中观尺度上的非平衡过程至关重要.
- 马库斯的过渡状态理论有效地描述了单步反应,但对连续化学状态空间中的多步过程有局限性.
研究的目的:
- 开发一种适用于多步反应系统的概括的随机马库斯状态模型.
- 将马库斯理论的适用性扩展到连续的化学状态空间.
主要方法:
- 使用延续方法开发一个随机马库斯状态模型.
- 使用福克-普朗克方程来描述概率密度函数的时间解析演变.
- 从自由能量函数和重组能量中确定漂移和扩散系数.
主要成果:
- 该模型通过福克-普朗克方程成功地描述了时间解析的概率密度函数.
- 对于具有无穷小的反应过渡的系统,确定了一个规模不变变换,保留了该模型的通用形式.
- 化学状态空间中的过度减弱的朗格温动力学被证明遵循波动-散流定理.
结论:
- 开发的随机马库斯状态模型为分析多步随机反应动态提供了一个框架.
- 这项研究证明了模型在经典的闭合近平衡系统中的通用性,在特定条件下检索 Onsager 相互关系.
相关概念视频
Multi-Step Reactions
8.6K
Chemical reactions often occur in a stepwise fashion involving two or more distinct reactions taking place in a sequence. A balanced equation indicates the reacting species and the product species, but it reveals no details about how the reaction occurs at the molecular level. The reaction mechanism (or reaction path) provides details regarding the precise, step-by-step process by which a reaction occurs. Each of the steps in a reaction mechanism is called an elementary reaction. These...
8.6K
Reaction Mechanisms
30.5K
Chemical reactions often occur in a stepwise fashion, involving two or more distinct reactions taking place in a sequence. A balanced equation indicates the reacting species and the product species, but it reveals no details about how the reaction occurs at the molecular level. The reaction mechanism (or reaction path) provides details regarding the precise, step-by-step process by which a reaction occurs.
For instance, the decomposition of ozone appears to follow a mechanism with two steps:
For instance, the decomposition of ozone appears to follow a mechanism with two steps:
30.5K
Entropy Change in Reversible Processes
3.2K
In the Carnot engine, which achieves the maximum efficiency between two reservoirs of fixed temperatures, the total change in entropy is zero. The observation can be generalized by considering any reversible cyclic process consisting of many Carnot cycles. Thus, it can be stated that the total entropy change of any ideal reversible cycle is zero.
The statement can be further generalized to prove that entropy is a state function. Take a cyclic process between any two points on a p-V diagram.
The statement can be further generalized to prove that entropy is a state function. Take a cyclic process between any two points on a p-V diagram.
3.2K
Standard Entropy Change for a Reaction
23.9K
Entropy is a state function, so the standard entropy change for a chemical reaction (ΔS°rxn) can be calculated from the difference in standard entropy between the products and the reactants.
23.9K
Mechanistic Models: Overview of Compartment Models
339
Mechanistic models, a category encompassing both physiological and compartmental modeling, differ from empirical models' approaches to incorporating known factors about the systems being modeled. Empirical models describe data with minimal assumptions, while mechanistic models aim to provide a robust description of available data by specifying assumptions and integrating known factors about the system. Compartmental analysis is a key example of a mechanistic model in pharmacokinetics and...
339
Parameters Affecting Nonlinear Elimination: Zero-Order Input, First-Order Absorption and Two-Compartment Model
275
Drugs administered through various routes can lead to nonlinear elimination, resulting in complex pharmacokinetic behaviors crucial to understanding efficacious drug dosing.
When a drug is administered through a constant intravenous infusion and eliminated via nonlinear pharmacokinetics, it follows zero-order input. For example, oral drugs undergo first-order absorption upon administration and are eliminated through nonlinear pharmacokinetics.
In the case of subcutaneously administered drugs,...
When a drug is administered through a constant intravenous infusion and eliminated via nonlinear pharmacokinetics, it follows zero-order input. For example, oral drugs undergo first-order absorption upon administration and are eliminated through nonlinear pharmacokinetics.
In the case of subcutaneously administered drugs,...
275


