Femtosecond experiments and absolute rate calculations on intervalence electron transfer of mixed‐valence compounds
Femtosecond experiments and absolute rate calculations on intervalence electron transfer of mixed‐valence compounds
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混合价化合物区间电子转移的飞秒实验和绝对速率计算
DOI：
10.1063/1.464344
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发表时间：
1993
影响因子：
4.4
通讯作者：
P. Barbara
中科院分区：
文献类型：
--
作者：
K. Tominaga;D. Kliner;Alan E. Johnson;N. Levinger;P. Barbara
报道了分子(NH_3)_5RuII(CN)−_5和(NH_3)_5FeII_(CRu)(CN)−_5的光学电子转移(ET)和随后的反向无辐射ET的新的实验结果和理论计算。利用这些参数，利用当代的ET模型计算了ET率。实验速率和理论速率在理论预测的不确定范围内是一致的，这是由于某些参数的不确定性造成的。结果表明，惯性溶质/溶剂相互作用和分子内快速能量涨落源对这些化合物的超快电子转移动力学起着重要作用。
New experimental results and theoretical calculations are reported for the optical electron transfer (ET) and subsequent reverse radiationless ET for the molecules (NH3)5RuIIINCRuII(CN)−5 and (NH3)5FeIIINCRuII(CN)−5. A procedure is presented for extracting many of the key parameters in ET theory from a combined analysis of resonance Raman data and the optical absorption ET band shape. Using these parameters, ET rates have been calculated using contemporary ET models. The experimental and theoretical rates agree within the uncertainty of the theoretical predictions, which results from an uncertainty in some of the parameters. The results demonstrate that inertial solute/solvent interactions and intramolecular sources of fast energy fluctuations play an important role in ultrafast ET kinetics for these compounds.
影响因子：
14.7
作者：
A. Warshel;W. W. Parson-W.
通讯作者：
A. Warshel;W. W. Parson-W.