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Studies on ultrafast reaction processes in solution and establishment of exciplex picosecond dynamics

溶液中超快反应过程研究及激基复合物皮秒动力学的建立

基本信息

批准号：
58430004
负责人：
MATAGA Noboru
金额：
$ 18.94万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (A)
财政年份：
1983
资助国家：
日本
起止时间：
1983 至 1985
项目状态：
已结题

项目摘要

(1) We have elucidated dynamic behaviors of exciplex systems and excited singlet EDA complexes in polar solvents by means of time-resolved emission, transient absorption and photocurrent measurements with picosecond (ps) and nanosecond (ns) laser photolysis methods.(2) We have confirmed that TMPD and related diamines in some polar solvents undergo photoinduced charge separation (CS) due to the electron transfer (ET) from fluorescent state to solvent cluster. Moreover, we have deteced ultrashort-lived ion pair produced by ET from Rydberg state pyrene to biphenyl in nonpolar solvent with ultraviolet ps multiphoton laser photolysis method.(3) We have elucidated the mechanism of the ultrafast nonradiative deactivation from the singlet ET state of porphyrin-quinone photosynthetic model systems and strong EDA complexes in polar solvents and have demonstrated the importance of the two step ET in porphyrin-quinone combined systems. Moreover, the mechanism of ultrafast nonradiative deactivation of <pai> -electronic hydrogen bonded systems have been elucidated.(4) We have established the method of ultraviolet ps multiphoton laser photolysis method for investigating the dynamics of excited and ionized states of molecular aggregates such as pure liquids and polymer films and have applied to alcohols, alkylbenzenes and alkanes.(5) We have elucidated the relation between the photoinduced intramolecular charge transfer and trans-cis isomerization of A-CH=CH-D type of compounds.(6) On the basis of above results of laser photolysis investigations, we have developed a new theory of the energy gap dependence of photoinduced CS and charge recombination reaction of produced radical ion pairs taking into consideration the large difference of the solvent photon frequency between the ionized and neutral state and have shown that the observed results can be interpreted satisfactorily by this theory.

(1)利用皮秒（ps）和纳秒（ns）激光光解方法，通过时间分辨发射、瞬态吸收和光电流测量，阐明了极性溶剂中激合体系和激发单线态EDA配合物的动力学行为。(2)我们证实了TMPD和相关的二胺在一些极性溶剂中由于电子从荧光态转移到溶剂簇而发生光诱导电荷分离（CS）。此外，我们还利用紫外多光子激光光解法检测了非极性溶剂中由里德堡态芘到联苯的ET产生的超短寿命离子对。(3)阐明了卟啉-醌光合模式体系和强EDA配合物在极性溶剂中单线态ET的超快非辐射失活机理，并证明了两步ET在卟啉-醌联合体系中的重要性。此外，还阐明了<pai> -电子氢键体系的超快非辐射失活机理。(4)建立了紫外多光子激光光解方法，用于研究纯液体和聚合物薄膜等分子聚集体的激发态和电离态动力学，并应用于醇类、烷基苯类和烷烃类。(5)阐明了A-CH=CH-D型化合物的光诱导分子内电荷转移与反式顺式异构化的关系。(6)在上述激光光解研究结果的基础上，考虑到溶剂光子频率在电离态和中性态之间的巨大差异，我们提出了光致CS和产生的自由基离子对的电荷复合反应的能隙依赖的新理论，并表明该理论可以令人满意地解释所观察到的结果。