RELATION BETWEEN CHARGE-TRANSFER ABSORPTION AND FLUORESCENCE-SPECTRA AND THE INVERTED REGION
RELATION BETWEEN CHARGE-TRANSFER ABSORPTION AND FLUORESCENCE-SPECTRA AND THE INVERTED REGION
复制标题
DOI：
10.1021/j100345a040
复制
发表时间：
1989-04-20
影响因子：
--
通讯作者：
MARCUS, RA
中科院分区：
文献类型：
--
作者：
MARCUS, RA
已知电荷转移 (CT) 带强度与频率关系图的理论表达式与电子转移速率常数 kET 与-AG 关系图的理论表达式相似。我们利用这种并行性来探索文献中的最新模型，该模型涉及溶剂的部分介电饱和对电子转移反应的“反转区域”的可能作用（如果有的话）。获得了 kET 和光谱图的半峰全宽的简单近似表达式，并使用计算出的 kET 与 AG 曲线的最新数值结果进行了测试。因此，使用 CT 带的实验宽度研究来测试关于部分介电饱和的可能存在和影响以及反转区域观察的想法。当吸收和荧光数据都可用时，电荷转移光谱的进一步用途也被描述，包括确定显示很少或没有振动结构的系统的“0-»0跃迁能量”AEq-^。
The theoretical expression for the plotof a charge transfer (CT) band intensity vs frequency is known to parallel that for the plot of electron-transfer rate constant kET vs-AG. We use this parallelism to explore a recent model in the literature on the possible role, if any, of partial dielectric saturation of the solvent on the “inverted region” of electron-transfer reactions. A simple approximateexpression is obtained for the full width at half-maximum for the kET and spectral plots and is tested using recent numerical results for calculated kET vs-AGcurves. Studies of experimental widths of CT bands are used, thereby, to test ideas on the possible presence and effects of partial dielectricsaturation and on the observation of the inverted region. Further uses of charge-transfer spectra, when both the absorption and fluorescence data are available, are alsodescribed, including the determination of the “0-» 0 transition energy” AEq-^ for systems displaying little or no vibrational structure.