Structural Dynamics of Phenyl Azide in Light-Absorbing Excited States： Resonance Raman and Quantum Mechanical Calculation Study  

苯基叠氮在光吸收激发态上的结构动力学一共振拉曼和量子力学计算研究

作　　者：袁荣单 薛佳丹[1] 郑旭明[1] 

机构地区：[1]浙江理工大学化学系,杭州310018

出　　处：《Chinese Journal of Chemical Physics》2016年第1期21-30,I0001,共11页化学物理学报（英文）

基　　金：This work is supported by the National Natural Science Foundation of China （No.21473163, No.21033002, No.21202032） and the National Basic Research Program of China （No.2013CB834604）.

摘　　要：The excited state structural dynamics of phenyl absorbing S2（A＇）, S3（A＇）, and S6（A＇） states were troseopy and complete active space self-consistent and the UV absorption bands were assigned on azide （PhN3） after excitation to the light studied using the resonance Raman specfield calculations. The vibrational spectra the basis of the Fourier transform （FT）- Raman, FT-infrared measurements, the density-functional theory computations and the normal mode analysis. The A-, B-, and C-bands resonance Raman spectra in cyclohex- ane, acetonitrile, and methanol solvents were, respectively, obtained at 273.9, 252.7, 245.9, 228.7, 223.1, and 208.8 nm excitation wavelengths to probe the corresponding structural dynamics of PhN3. The results indicated that the structural dynamics in the S2 （A＇）, S3（A＇）, and S6（A＇） states were significantly different. The crossing points of the potential energy surfaces, S2S1（1） and S2S1（2）, were predicted to play a key role in the low-lying excited state decay dynamics, in accordance with Kasha＇s rule, and NT=N8 dissociation. Two decay channels initiated from the Franck-Condon region of the S2（A＇） state were predicted： the radiative S2,min→S0 radiative decay and the S2→S1 internal conversion through the crossing points S2S1 （1）/S2S1（2）.

关 键 词：Phenyl azide Structural dynamics Decay dynamics Resonance Raman spec- troscopy CASSCF calculation Curve-crossing 

分 类 号：O[理学]