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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Large Electron Transfer Rate Effects from the Duschinsky Mixing of Vibrations
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Large Electron Transfer Rate Effects from the Duschinsky Mixing of Vibrations

机译：Duschinsky振动混合对大电子传递速率的影响

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摘要

We systematically test how the Duschinsky mixing of normal coordinate vibrations affects transition rates for electron transfer (ET). We find that ET rates in the inverted region can increase many orders of magnitude from Duschinsky mixing, and both totally symmetric and nontotally symmetric vibrations are very important.The Duschinsky effect arises when two electronic states have vibrational normal mode coordinate systems that are rotated and translated relative to each other. We use a conventional quantum rate model for ET, and the examples include 6-8 vibrations, where two vibrational modes are mixed with different amounts of coordinate rotation. The multidimensional Franck-Condon factors (FCF) are computed with standard algorithms and recently developed recursion relations. When displaced, totally symmetric modes are involved,rates with Duschinsky mixing can increase several orders of magnitude for inverted electron transfer reactions and modest mixing. The peak location in a rate vs energy gap plot can depend on the degree of Duschinsky mixing, and therefore it corresponds to a sum of solvent and an effective vibrational reorganization energy that is not predictable by simple models that exclude mixing. In addition, for some examples of inverted region ET we observe significant flattening of the usual parabolic curve at large degrees of mixing. We demonstrate that large rate effects can occur with very little change in either the calculated absorption or emission spectra, depending on the details of the Duschinsky mixing. The origin of the rate effect is the increased FCF between the initial vibrational state and the higher lying final vibrational states when the Duschinsky effect is taken into account. The rate effect of totally symmetric modes is greater than nontotally symmetric modes, but since there are many nontotally symmetric modes, in real molecules these modes can make a large total contribution to ET rates.
机译：我们系统地测试了法向坐标振动的Duschinsky混合如何影响电子转移（ET）的跃迁速率。我们发现，由于Duschinsky混合，反向区域的ET速率可以增加许多数量级，并且完全对称和非完全对称的振动都非常重要。当两个电子态具有振动的平模坐标系进行旋转和平移时，Duschinsky效应产生相对于彼此。我们将常规的量子速率模型用于ET，示例包括6-8次振动，其中两种振动模式混合了不同的坐标旋转量。多维Franck-Condon因子（FCF）使用标准算法和最近开发的递归关系进行计算。当发生位移时，将涉及完全对称的模态，对于反向电子转移反应和适度的混合，Duschinsky混合的速率可以增加几个数量级。速率与能隙图的峰值位置可能取决于Duschinsky混合的程度，因此，它对应于溶剂和有效的振动重组能之和，这是无法通过排除混合的简单模型来预测的。此外，对于倒置区域ET的一些示例，我们观察到在较大的混合度下，通常的抛物线会显着变平。我们证明，根据Duschinsky混合的细节，在计算的吸收光谱或发射光谱中几乎没有变化的情况下，可以发生较大的速率效应。速率效应的起因是，当考虑了Duschinsky效应时，初始振动状态和较高的最终振动状态之间的FCF增大。完全对称模式的速率效应大于非完全对称模式，但是由于存在许多非完全对称模式，因此在实际分子中，这些模式可以对ET速率做出很大的贡献。

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