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arXiv 1607.07010cond-mat.mes-hallcond-mat.stat-mech
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热梯度电子转移

Electron transfer across a thermal gradient

Galen T. Craven, Abraham Nitzan

摘要:

电荷转移是化学和生物学中许多现象的基础过程。最近的进展,在纳米尺度上观察和操纵电荷和热传输,最近开发的技术,用于监测温度在高的时间和空间分辨率,意味着需要考虑跨热梯度的电子转移。在这里,一个理论的电子转移速率和相关的热传输之间的供体-受体对位于不同温度的网站。为此,通过应用一个广义的多维过渡态理论,作为一个自由能表面上的一个单一的点的活化能的传统的阿克里尼乌斯图片被替换为一个bithermal属性,来自统计加权所有配置的反应物和产物状态是等能的。与电子转移过程相关的能量流也被检查,导致作为温差和电子驱动偏压的函数的供体和受体位点之间的热交换速率之间的关系。特别是,我们发现,一个开放的电子转移通道有助于增强网站之间的热传输,即使当它们处于电子平衡。所提出的结果提供了一个统一的理论电荷传输和相关的热传导网站之间在不同的温度。

英文摘要:

Charge transfer is a fundamental process that underlies a multitude of phenomena in chemistry and biology. Recent advances in observing and manipulating charge and heat transport at the nanoscale, and recently developed techniques for monitoring temperature at high temporal and spatial resolution, imply the need for considering electron transfer across thermal gradients. Here, a theory is developed for the rate of electron transfer and the associated heat transport between donor-acceptor pairs located at sites of different temperatures. To this end, through application of a generalized multidimensional transition state theory, the traditional Arrhenius picture of activation energy as a single point on a free energy surface is replaced with a bithermal property that is derived from statistical weighting over all configurations where the reactant and product states are equienergetic. The flow of energy associated with the electron transfer process is also examined, leading to relations between the rate of heat exchange among the donor and acceptor sites as functions of the temperature difference and the electronic driving bias. In particular, we find that an open electron transfer channel contributes to enhanced heat transport between sites even when they are in electronic equilibrium. The presented results provide a unified theory for charge transport and the associated heat conduction between sites at different temperatures.

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。

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