论文标题
构象动力学调节电子传递
Conformational dynamics modulating electron transfer
论文作者
论文摘要
电子转移反应中供体距离距离的扩散动力学是导致在电子隧道降低距离内扩散的新时间尺度的原因。距离动力学与溶剂控制的电子传输动力学中的中偏振动力学竞争。提出了一种将介质和供体 - 受体动力学纳入电子转移速率常数的新溶液。速率常数开关的指数因子在距离无关的溶剂控制状态和指数距离衰减之间。两个机制之间的交叉由有效的松弛时间缩短，这是根据供体 - 受体位移的方差呈指数变化的速度。柔性供体 - 受体配合物必须显示出更大的溶剂控制电子转移趋势。电子转移能量链是最好通过将氧化还原辅助因子放在交叉距离附近的设计而设计的。
Diffusional dynamics of the donor-acceptor distance in electron-transfer reactions are responsible for the appearance of a new time scale of diffusion over the distance of falloff of electronic tunneling. The distance dynamics compete with the medium polarization dynamics in the solvent-controlled electron transfer kinetics. A new solution incorporating the medium and donor-acceptor dynamics into the electron-transfer rate constant is proposed. The pre-exponential factor of the rate constant switches between a distance-independent solvent-controlled regime and exponential distance decay. The crossover between two regimes is controlled by an effective relaxation time slowed down by a factor exponentially depending on the variance of the donor-acceptor displacement. Flexible donor-acceptor complexes must show a greater tendency for solvent-controlled electron transfer. Electron-transfer energy chains are best designed by placing the redox cofactors near the crossover distance.
