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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Common Marcus Type Dependence of the Charge Transfer Induced Processes in the Sensitization and Quenching of Singlet Oxygen by Naphthalene Derivatives
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Common Marcus Type Dependence of the Charge Transfer Induced Processes in the Sensitization and Quenching of Singlet Oxygen by Naphthalene Derivatives

机译:萘衍生物对单态氧的敏化和猝灭过程中电荷转移诱导过程的常见马库斯类型依赖性

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摘要

The charge-transfer induced quenching processes of the lowest excited triplet state (T_1) of naphthalene derivatives by ground-state oxygen and of singlet oxygen O_2(~1 #DELTA#_g) by ground state naplithalene derivatives have been investigated in three solvents of different polarity. Both deactivation processes are described by one common Marcus type plot. The analysis of the data strongly indicates that exciplexes with the same degree of average partial charge transfer (pCT) and the same reorganization energy are formed in the rate-determining step of both quenching processes. The free energies of pCT complex formation are related to the corresponding free energy of complete electron transfer by #DELTA#G_(CT)=f #DELTA#G_(CET) with a common corrective factor f, for T_1 and O_2(~1 #DELTA#_g) deactivation. The reorganization energy increases from 34 kJ mol~(-1) in carbon tetrachloride to 92 kJ mol~(-1) in acetonitrile. The charge transfer character is shown to be significantly larger than 25% and to increase with increasing solvent polarity.
机译:在三种不同溶剂中研究了基态氧对萘衍生物的最低激发三重态(T_1)和基态萘并萘对单态氧O_2(〜1#DEL#_g)的电荷转移诱导猝灭过程极性。两种停用过程均由一个常见的Marcus类型图描述。数据分析强烈表明,在两个猝灭过程的速率确定步骤中,形成了具有相同程度的平均部分电荷转移(pCT)和相同的重组能量的激基复合物。对于T_1和O_2(〜1#),pCT配合物形成的自由能与具有共同校正因子f的#DELTA#G_(CT)= f#DELTA#G_(CET)的电子完全转移的相应自由能有关。 DELTA#_g)停用。重组能从四氯化碳中的34 kJ mol〜(-1)增加到乙腈中的92 kJ mol〜(-1)。电荷转移特性显示出明显大于25%,并且随着溶剂极性的增加而增加。

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