A rate constant expression for charge transfer through fluctuating bridges
A rate constant expression for charge transfer through fluctuating bridges
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DOI：
10.1063/1.1601600
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发表时间：
2003-09
影响因子：
4.4
通讯作者：
A. Troisi;A. Nitzan;M. Ratner
中科院分区：
文献类型：
--
作者：
A. Troisi;A. Nitzan;M. Ratner
柔性桥介导的电荷转移反应的速率常数的表达式作为一系列的条款的重要性递减。前导项对应于从Condon近似获得的静态极限。由于有限时间波动的校正明确评估，假设高斯形状的耦合自相关函数和马库斯模型与一维谐波热浴。使用该模型的解释实验数据和预期的波动效应的幅度进行了讨论。
A rate constant expression for charge transfer reactions mediated by flexible bridges is presented as a series of terms of decreasing importance. The leading term corresponds to the static limit obtained from the Condon approximation. Corrections due to finite time fluctuations are evaluated explicitly, assuming a Gaussian shape of the coupling autocorrelation function and the Marcus model with a one-dimensional harmonic thermal bath. The use of this model for the interpretation of experimental data and the expected magnitudes of the fluctuation effects are discussed.