Non-Equilibrium Thermodynamics formalism for Marcus cross-exchange electron transfer reaction rates
Richa Sethi, M. V. Sangaranarayanan
利用Onsager非平衡态热力学理论推导了Marcus理论中的交叉交换电子转移公式。
The cross-exchange electron transfer expression arising from Marcus theory is deduced using Onsager's non-equilibrium Thermodynamics formalism.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
继续探索
In the pioneering work by R. A. Marcus, the solvation effect on electron transfer (ET) processes was investigated, giving rise to the celebrated nonadiabatic ET rate formula. In this work, on the basis of the thermodynamic solvation potentials analysis, we reexamine Marcus' formula with respect to the Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Interestingly, the obtained RRKM analogue, which recovers the original Marcus' rate that is in a linear solvation scenario, is also applicable to the nonlinear solvation scenarios, where the multiple curve{crossing of solvation potentials exists. Paral…
Electron transfer organic reaction rates are considered employing the classic physical picture of Marcus wherein the heats of reaction are deposited as the energy of low frequency mechanical oscillations of reconfigured molecular positions. If such electron transfer chemical reaction events occur in the neighborhood of metallic plates, then electrodynamic interface fields must also be considered in addition to mechanical oscillations. Such electrodynamic interfacial electric fields in principle strongly effect the chemical reaction rates. The thermodynamic states of the metal are unchanged by …
Resolving the Marcus-Rehm-Weller Paradox in Electron Transfer
本文通过两能级量子哈密顿量揭示Marcus和Rehm-Weller动力学的物理极限，展示了在正常区和倒置区的不同行为，无需引入扩散限制或现象修正即可定量再现Rehm-Weller数据。
Charge transport through molecular junctions is often described either as a purely coherent or a purely classical phenomenon, and described using the Landauer-Büttiker formalism or Marcus theory, respectively. Using a generalised quantum master equation, we here derive an expression for current through a molecular junction modelled as a single electronic level coupled to a collection of thermalised vibrational modes. We demonstrate that the aforementioned theoretical approaches can be viewed as two limiting cases of this more general expression, and present a series of approximations of this r…
Beyond the dielectric continuum description initiated by Marcus theory, the nowadays standard theoretical approach to study electron transfer (ET) reactions in solution or at interfaces is to use classical force field or ab initio Molecular Dynamics simulations. We propose here an alternative method based on liquid-state theory, namely molecular density functional theory, which is numerically much more efficient than simulations while still retaining the molecular nature of the solvent. We begin by reformulating molecular ET theory in a density functional language and show how to compute the v…
Direct simulation of electron transfer using ring polymer molecular dynamics: Comparison with semiclassical instanton theory and exact quantum methods
使用环状聚合物分子动力学（RPMD）的电子转移（ET）反应动力学的直接模拟马库斯理论，半经典瞬子理论，和精确的量子动力学方法的背景下进行了分析。对于完全原子和系统浴表示的凝聚相ET，我们证明了RPMD准确地预测ET反应速率和整个正常和activationless制度的热力学驱动力的机制。反应RPMD轨迹的系综分析揭示了溶剂重组机制的ET，预计在马库斯率理论，和RPMD率计算的准确性被理解的统计波动和其正式连接到半经典瞬子理论的深隧穿过程的精确描述。在热力学驱动力的倒置机制中，RPMD和半经典瞬子理论的相关公式都不能捕捉到反应速率的特征周转率;与精确的量子动力学模拟相比，这些方法在倒置机制中对实时电子态动力学的量化不足。
Theory of Chemical Kinetics and Charge Transfer based on Nonequilibrium Thermodynamics
化学动力学的经典理论假设稀溶液中的独立反应，其速率由平均浓度决定。在凝聚态物质中，强相互作用会改变化学活性并产生不均匀性，从而显著影响反应速率。极端的情况是反应耦合到相变，其动力学必须依赖于序参量-和它的梯度，在相边界。本文介绍了一种以非平衡态热力学为基础的化学动力学的一般理论。反应速率是以变化的化学势表示的热力学驱动力（反应自由能）的非线性函数。通过一个非平衡化学热力学主方程，将Cahn-Hilliard方程和Allen-Cahn方程统一并推广。对于电化学，Marcus和Butler-Volmer动力学都适用于浓溶液和离子固体。将该理论应用于相分离锂离子电池材料Li $_x$ FePO $_4$中的嵌入动力学。
Macroscopic entropy production $σ^{(tot)}$ in the general nonlinear isothermal chemical reaction system with mass action kinetics is decomposed into a free energy dissipation and a house-keeping heat: $σ^{(tot)}=σ^{(fd)}+σ^{(hk)}$; $σ^{(fd)}=-\rd A/\rd t$, where $A$ is a generalized free energy function. This yields a novel nonequilibrium free energy balance equation $\rd A/\rd t=-σ^{(tot)}+σ^{(hk)}$, which is on a par with celebrated entropy balance equation $\rd S/\rd t=σ^{(tot)}+η^{(ex)}$ where $η^{(ex)}$ is the rate of entropy exchange with the environment.For kinetic systems with complex …
Electron Transfer (ET) reactions are modeled by the dynamics of a quantum two-level system (representing the electronic state) coupled to a thermalized bath of classical harmonic oscillators (representing the nuclei degrees of freedom). Unlike for the standard Marcus theory, the complex amplitudes of the electronic state are chosen as reaction coordinates. Then, the dynamical equations at non vanishing temperature become those of an effective Hamiltonian submitted to damping terms and their associated Langevin random forces. The advantage of this new formalism is to extend the original theory …
Diffusion in Evaporating Polymer Solutions: A Model in the Dissipative Formalism of Nonequilibrium Thermodynamics
本文在非平衡热力学的框架内，将溶剂蒸发过程中聚合物溶液中的扩散过程建模为一个具有移动边界条件的热质耦合问题。从经典热力学基本方程出发，利用局部平衡假设推导出的控制方程，比以往的研究工作显示出更复杂的热量和非对流质量通量之间的联系。数值计算，使用显式有限差分格式进行，表明该模型能够捕捉聚合物溶液中的热扩散的效果。这种效应本身表现为在溶液浇铸过程中靠近热基底的溶剂局部浓度的增加。
This paper studies a mathematical formalism of nonequilibrium thermodynamics for chemical reaction models with $N$ species, $M$ reactions, and general rate law. We establish a mathematical basis for J. W. Gibbs' macroscopic chemical thermodynamics under G. N. Lewis' kinetic law of entire equilibrium (detailed balance in nonlinear chemistry kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic models are represented by a Markovian jumping process. A generalized macroscopic chemical free energy functi…
Onsager's phenomenological equations successfully describe irreversible thermodynamic processes. They assume a symmetric coupling matrix between thermodynamic fluxes and forces. It is easily shown that the antisymmetric part of a coupling matrix does not contribute to dissipation. Therefore, entropy production is exclusively governed by the symmetric matrix even in the presence of antisymmetric terms. In this work we focus on the antisymmetric contributions which describe isentropic oscillations and well-defined equations of motion. The formalism contains variables that are equivalent to momen…
Quantum Thermodynamics of Electron Transport along Chains of Redox Centers
研究生物系统中分子内电子传输，通过林德布拉德方程扩展量子力学模型到氧化还原中心长链，探索物理参数，关注电子与蛋白质浴热和熵传递，明确表征电子电流等，展现多域蛋白质结构电子输运关键特征。
扫码添加微信好友，提出您的宝贵建议 👇
💡 备注请填写：网站反馈
发表机构由 AI 从论文文本抽取，如发现错误，欢迎反馈修正建议。