酞菁和卟啉分子的超快内转换和振动弛豫

用微扰密度矩阵和瞬态线性极化率理论，模拟了四特丁基酞菁（BuPc）和四苯基卟啉（TPP）分子的飞秒荧光亏蚀谱．初步定量地确定了它们的Huang-Rhys因子．振动弛豫和电子激发态溶剂化的速率常数．飞秒荧光亏蚀谱在零延时附近的尖峰．归结为S2→S1的内转换所造成的后果．通过对光谱的模拟，比较可靠地确定了内转换速率常数。

Ultrafast Internal Conversion and Vibrational Relaxation of Butylphthalocyanine and Tetraphenylporphyrin in Solution

Ultrafst internal conversion (IC) and vibrational relaxation dynamics of electronically excited butylphthalocyanine (BuPc ) and tetra-phenylporpyrin (TPP ) molecules in solution are theoretically studied on the basis of the perturbative density operaor method and the transien linear susceptibility theory. Femtosecond time-resolved profile of fluorescence depetion is simulated with a single vibrational mode. The intemal conversion, the vibrational relaxation and the solvation rate constants in electronically excited states are detendned. The results show that the sharp peak of fluorescence depletion reflects primarily the internal conversion process from the S2 state to the S1 state of BuPc and TPP.IC occurs in a 200 fs time scale.