Effect of laser intensity on the determination of intermolecular electron transfer rate constants—Observation of Marcus inverted region in photoinduced back electron transfer reactions
| Autor: | Yuxiang Weng, Kwok-Chu Chan, Chi-Ming Che, Biing-Chiau Tzeng |
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| Rok vydání: | 1998 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 109:5948-5956 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.477219 |
| Popis: | The light intensity and concentration dependence of the photoproduct yield are investigated in a monophotonic process. The relationship of the photoproduct yield with the laser intensity and the complex concentration for a monophotonic process is derived under laser flash photolysis. The relationship is confirmed experimentally in a monophotonic process, i.e., triplet–triplet transition for a Cu(I) complex Cu6(DMNSN′)6 (DMNSN′=4,6-dimethylpyrimidine-2-thiolate). At low light intensity, the relationship can be approximated by a linear inverse square root dependence on the light intensity. Based on this equation, a method is proposed to determine the intrinsic back electron transfer rate constant kETb in photoinduced intermolecular electron transfer reactions, precluding the effect from the diffusional encounter pairs. The Marcus “inverted region” is observed by using the method in photoinduced back electron transfer reactions of [Au2(dppm)2](ClO4)2 (dppm=bis(diphenylphosphino)methane) with a series of subs... |
| Databáze: | OpenAIRE |
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