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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Temperature Dependence of the Outer-Sphere Reorganization Energy
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Temperature Dependence of the Outer-Sphere Reorganization Energy

机译：外层重组能量的温度依赖性

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摘要

The temperature dependence of the intervalence charge transfer transition (IT) has been studied for a mixed-valence dinuclear iron complex. The two "halves" of this complex consist of trisbipyridineiron moieties that are triply linked with saturated alkyl chains. Because the complex is symmetric, the energy of the IT band is a direct measure of the reorganization energy for electron transfer between the two irons. Moreover, for the specific complex under investigation here, the inner-sphere reorganization energy is essentially zero because of an exact cancellation of sigma- and pi-bonding changes upon changing the oxidation state of each iron. As a consequence, the energy of the IT transition is a direct measure of the outer-sphere (solvent) reorganization energy. The energy of the IT band has been investigated over the temperature range -28 deg C to 30 deg C. The derivative of the outer-sphere reorganization energy with respect to temperature found from this study was -3.2 +- 0.4 cm~(-1)K~(-1). Theoretical calculations based on the Marcus two spheres in a dielectric continuum model and a molecular based model developed by Matyushov were also carried out for comparison with the experimental results. The continuum model predicts a positive slope for the derivative while the Matyushov model gives a negative slope that differs from that of the experimental data by a factor of approx 2 in magnitude.
机译：已经研究了混合价双核铁配合物的间隔电荷转移跃迁（IT）的温度依赖性。该复合物的两个“半”由三联吡啶铁部分组成，三联吡啶铁部分与饱和烷基链相连。因为络合物是对称的，所以IT谱带的能量是两个铁之间电子转移的重组能的直接量度。此外，对于这里正在研究的特定复合物，由于在改变每种铁的氧化态时，σ和pi键变化的准确抵消，内球的重组能基本上为零。结果，IT转换的能量是外层（溶剂）重组能量的直接度量。已在-28℃至30℃的温度范围内研究了IT波段的能量。根据这项研究发现，外层重组能量相对于温度的导数为-3.2 +-0.4 cm〜（-1 ）K〜（-1）。还进行了基于介电连续体模型中的马库斯两个球体和Matyushov开发的基于分子的模型的理论计算，以与实验结果进行比较。连续模型预测导数为正斜率，而Matyushov模型给出的负斜率与实验数据相差大约2倍。

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