Intermolecular Dynamics and Exciplex Formation of van der Waals Complexes

1.在无碰撞条件下研究了1-氰基萘/三乙胺货车范德华复合物激发时的激基复合物形成动力学。发现vdW配合物S_1态分子内和分子间振动模式之间的结合带的激发具有模式特异性，从而促进了激基复合物的形成反应，并测量了S_1和激基复合物态的荧光衰减随S_1以上过剩能量的变化。用一个简单的动力学模型讨论了所观察到的衰变速率常数.在超声膨胀产生的芴和9-乙基芴的货车范德华二聚体和异二聚体的激发下，获得了激基缔合物和激基复合物的荧光光谱和衰减时间。激基复合物的光谱最大值和衰减时间几乎介于芴和9-乙基芴两种激基缔合物之间。vdW异二聚体向激基复合物的转变发生在异二聚体的激发态，对应于9-乙基芴的局部激发态.在超音速自由射流中观察到了1-氰基-4-甲基萘与三乙胺形成的两种类型的货车范德华络合物。在激发这些复合物的原始谱带时，从其中一个复合物中观察到分散的激基复合物荧光，而从另一个复合物中没有检测到明显的激基复合物荧光。然而，荧光激发光谱表明，这些复合物的激基复合物的转换过程中进行的激发到更高的振动状态。从VDW复合物的激基复合物formation也表明这些喷射冷却物种的荧光衰减时间的测定。

1. The exciplex formation dynamics of the 1-cyanonaphthalene/triethylamine van der Waals complex upon excitation has been examined under collision free condition. Mode-specificity has been found in the excitation of a combination band between intra- and intermolecular vibrational modes in the S_1 state of the vdW complex to promote the exciplex formation reaction.The fluorescence decays of the S1 and exciplex states have been measured as a function of excess energy above the S1 origdn. The observed decay rate constants have been discussed using a simple kinetic model.2. Upon excitation of the van der Waals dimer and heterodimer of fluorene and 9-ethylfluorene generated in a supersonic expansion, the excimer and exciplex fluorescence spectra and decay times were obtained, The spectral maximum and decay time of the exciplex are almost intermediate between two excimers of fluorene and 9-ethylfluorene. The transformation of vdW heterodimer to the exciplex takes place from the excited state of the heterodimer corresponding to the locally excited state of 9-ethylfluorene.3. Two types of van der Waals complexes between 1-cyano-4-methylnaphthalene and triethylamine were obvserved in the supersonic free jet. Upon excitation of neraly origin bands of these complexes, the dispersed exciplex fluorescence was observed from one of the complexes, while no significnat exciplex fluorescence was detected from the other complex. However, the fluorescence excitation spectra demonstrate that the transformation to the exciplex proceeds in the excitation to the uper vibrational state of these complexes. The exciplex fromation from the vdW complex was also indicated by the determination of fluorescence decay times of these jet cooled species.