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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A Theory of Electron Transfer and Steady-State Optical Spectra of Chromophores with Varying Electronic Polarizability
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A Theory of Electron Transfer and Steady-State Optical Spectra of Chromophores with Varying Electronic Polarizability

机译：电子极化率变化的发色团的电子转移和稳态光谱理论

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摘要

Electron transfer (ET) reactions and optical transitions are considered in chromophores with both the dipole moment and the electronic polarizability varying with the transition. An exact solution for reaction free energy surfaces of ET along a reaction coordinate has been obtained in the Drude model for the solute and solvent polarizabilities. The ET surfaces manifest the following effects of a nonzero polarizability variation: they (i) are asymmetric, (ii) have different curvatures at their minima, and (iii) become infinite for reaction coordinates outside a one-sided fluctuation band. The physical origin of these effects is the renormalization of the solute dipole by the solvent reaction field depending on the nonequilibrium solvent configuration. The reorganization energies of ET are substantially different for forward and backward transitions with higher reorganization energy in the state with hider solute polarizability. The dependence of the ET rate on the equilibrium energy gap is quadratic near the rate maximum and is linear at large energy gaps. The energy gap curves are also flatter from the side of exothermic reactions and broader for the state with a higher polarizability. The bandshape analysis of optical transitions is extended to the case of a nonzero polarizability variation.
机译：发色团中考虑了电子转移（ET）反应和光学跃迁，偶极矩和电子极化率均随跃迁而变化。在溶质和溶剂极化率的Drude模型中，已经获得了沿着反应坐标的ET反应自由能表面的精确解。 ET表面表现出以下非零极化率变化的影响：它们（i）不对称，（ii）在其最小值处具有不同的曲率，并且（iii）对于单侧波动带之外的反应坐标来说是无限的。这些影响的物理原因是溶质偶极子会根据溶剂的非平衡构型而通过溶剂反应场重新归一化。在具有脂质溶质极化性的状态下，ET的重组能量对于向前和向后跃迁具有显着不同的更高重组能量。 ET速率对平衡能隙的依赖性在速率最大值附近呈二次关系，在大能隙处呈线性关系。从放热反应的角度来看，能隙曲线也较平坦，对于极化率较高的状态，能隙曲线也较宽。光学跃迁的带状分析扩展到非零极化率变化的情况。

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