電子励起緩和過程を支配する熱平衡分布と活性化エネルギーの物理化学的意味

控制电子激发弛豫过程的热平衡分布和活化能的物理化学意义

• 批准号: 06453024
• 负责人: HIRAYAMA Satoshi
• 金额: $ 4.35万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06453024/
• 关键词: 9-cyanoanthracene; Activation energy; van der Waals complexes; Supersonic free jet; Thermal activation; Partially cooled states; Dark states; Laser free spectroscopic measurements; 高分解能分光システム; 超臨界流体; 熱的励起; 重原子効果

We have successfully developed a simple but powerful technique by which the absorption and fluorescence excitation spectra of isolated or van der Waals complexes generated in supersonic jets can be measured simultaneously.The technique, which dispenses with any laser and is achieved for the first time in the world (Rev.Sci.Instrum., in press), will allow one to explore a new field of molecular relaxation dynamics, in particular, in which dark states or non-emissive levels play a decisive role.Intensive studies have been carried out on the following four subjects by using the developed technique. We have obtained extremely exciting results on each subject.1.State selective relaxation processes and thermal activation. We have already submitted a paper entitled "Thermal energy assisted heavy atom effect-Fluorescence quenching of 9-cyanoanthracene in supercritical fluid of Xe".2.Fluorescence quenching of anthracene derivatives and van der Waals complex formation with oxygen.3.Non-radiative processes of non-fluorescent anthracenes.4.Electronic relaxation processes from partially cooled states (PCS). The idea of PCS was introduced by us many years ago. The present technique is found to provide us novel information about PCS.

我们已经成功地开发了一种简单而强大的技术，通过它可以同时测量在超音速射流中产生的孤立或范德华配合物的吸收和荧光激发光谱。该技术无需任何激光，在世界上尚属首次（rev . sci . instrument）。，将允许人们探索分子弛豫动力学的新领域，特别是在暗态或非发射能级起决定性作用的领域。利用开发的技术，对以下四个主题进行了深入的研究。我们在每门学科上都取得了令人兴奋的成绩。状态选择松弛过程和热激活。我们已经提交了一篇题为“热能辅助重原子效应- 9-氰蒽在Xe超临界流体中的荧光猝灭”的论文。蒽衍生物的荧光猝灭及与氧形成范德瓦尔斯络合物。非荧光蒽的非辐射过程。部分冷却态的电子弛豫过程。pc的概念是我们多年前提出的。本技术为我们提供了有关PCS的新信息。

项目成果

F.TANAKA et al.: "Pressure and temperature dependences of the rate constant for S_1-T_2 intersystem crossing of anthracene compounds in solution" J.Phys.Chem.99. 525-530 (1995)

F.TANAKA 等人：“溶液中蒽化合物的 S_1-T_2 系间窜越速率常数的压力和温度依赖性”J.Phys.Chem.99。

F.TANAKA et al.: "Effects of clustering of rare-gas atoms on the rate of S_1-T_2 intersystem crossing for 9-methylanthracene" Chemical Physics Letters. (in press).

F.TANAKA 等人：“稀有气体原子聚集对 9-甲基蒽 S_1-T_2 系间窜越速率的影响”《化学物理快报》。

U.Graf: "Laser free measurements of absorption and fluorescence excitation spectra in a supersonic ferr jet" Review of Scientific Instruments. (in press). (1996)

U.Graf：“超音速 Ferr 喷射中吸收和荧光激发光谱的无激光测量”科学仪器评论。

F. TANAKA,et al.: "Pressure and temperature dependences of the rate constant for S_1-T_2 intersystem crossing of anthracene compounds in solution" J. Phys. Chem.99. 525-530 (1995)

F. TANAKA 等人：“溶液中蒽化合物 S_1-T_2 系间窜越的速率常数的压力和温度依赖性”J. Phys。

S. HIRAYAMA,et al.: "Energy and state selective electronic relaxation of anthracene derivatives and their van der Waals complexes-An attempt to link dynamics in gas phase and solution" Trends in photochemistry & Photobiology. 3. 549-579 (1994)

S. HIRAYAMA 等人：“蒽衍生物及其范德华配合物的能量和状态选择性电子弛豫 - 连接气相和溶液动力学的尝试” 光化学趋势