Spectral Shift of π→π^＊ Transition for p-Nitroaniline Based on a New Expression of Nonequilibrium Solvation Energy  

基于约束非平衡溶剂化理论的对硝基苯胺π→π^＊光谱移动

作　　者：季健[1] 任海生[1] 马建毅[2] 李象远[3] 

机构地区：[1]四川大学化学学院,成都630064 [2]四川大学原子分子所,成都630065 [3]四川大学化工学障,成都630065

出　　处：《Chinese Journal of Chemical Physics》2014年第2期181-188,I0003,I0004,共10页化学物理学报（英文）

基　　金：ACKNOWLEDGMENTS This work was supported Science Foundation of China by the National Natural （No.91016002）.

摘　　要：According to the nonequilibrium solvation theory studies, a constrained equilibrium principle is introduced and applied to the derivations of the nonequilibrium solvation energy, and a reasonable expression of the spectral shift of the electronic absorption spectra is deduced. Furthermore, the lowest transition of p-nitroaniline （pNA） in water is investigated by time-dependent density functional theory method. In addition, the details of excited state properties of pNA are discussed. Using our novel expression of the spectral shift, the value of -0.99 eV is obtained for π→π^＊ transition in water, which is in good agreement with the available experimental result of -0.98 eV.

关 键 词：Nonequilibrium solvation theory Spectral shift Solvent reorganization energy Constrained equilibrium 

分 类 号：R-33[医药卫生]