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首页> 外文期刊>Chemistry: A European journal >Multiple Mechanisms for Electron Transfer at Metal/Self-Assembled Monolayer/Room-Temperature Ionic Liquid Junctions: Dynamical Arrest versus Frictional Control and Non-Adiabaticity
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Multiple Mechanisms for Electron Transfer at Metal/Self-Assembled Monolayer/Room-Temperature Ionic Liquid Junctions: Dynamical Arrest versus Frictional Control and Non-Adiabaticity

机译：金属/自组装单层/室温离子液体结处电子转移的多种机制：动态阻滞与摩擦控制和绝热

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摘要

Electrochemical devices consisting of gold electrodes coated by electronically well-behaved self-assembled alkanethiol monolayers of variable thickness, a ferrocene/ferrocenium redox probe and a typical room-temperature ionic liquid (RTIL) [bmim]- ACHTUNGTRENUNG[NTf2] (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) as a unique reaction medium with an exceptionally broad spectrum of relaxational modes (probed under variable temperature and pressure conditions), have been used to vary the intrinsic electron- transfer (ET) rate constant over eight orders of magnitude (from 0.1 to 3×10~7 s~(-1)) by further tuning of the overvoltage. A remarkable interplay of ET mechanisms was observed, which was accompanied by the stepwise drop in the reorganisation free energy of the medium from 1.0 to 0.1 eV. The first mechanistic changeover to the dynamically arrested regime, with a locking ultra-slow relaxation time of approximately 50 ms, occurred at donor–acceptor separations below 20 A. Another mechanistic changeover to the full solvent friction regime, controlled by a medium relaxation process of approximately 100 ns, emerged for ET distan-ces smaller than 8 A.
机译：电化学装置由金电极组成，该金电极涂覆有可变厚度的行为良好的自组装烷硫醇电子自组装单分子膜，二茂铁/二茂铁氧化还原探针和典型的室温离子液体（RTIL）[bmim]-ACHTUNGTRENUNG [NTf2]（1-丁基-3-甲基咪唑双（三氟甲基磺酰基）酰亚胺作为一种独特的反应介质，具有极宽的弛豫谱谱（在可变的温度和压力条件下进行测试），已被用于改变八种以上的固有电子传递（ET）速率常数通过进一步调节过电压将其数量级提高（从0.1到3×10〜7 s〜（-1））。观察到ET机制的显着相互作用，同时伴随着介质重组自由能从1.0 eV逐步下降到0.1 eV。在低于20 A的供体-受体间距下，发生了首次向动态停止状态的机械转换，锁定超慢弛豫时间约为50 ms。另一次向全溶剂摩擦状态的机械转换由中等弛豫过程控制对于小于8 A的ET距离出现大约100 ns。

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