Explicit solvent model for spectral shift of acrolein and simulation with molecular dynamics  

作　　者：ZHU Quan LIU Jifeng FU Kexiang HAN Keli LI Xiangyuan 

机构地区：[1]College of Chemical Engineering, Sichuan University, Chengdu 610065, China [2]Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

出　　处：《Chinese Science Bulletin》2006年第24期2951-2958,共8页

基　　金：Acknowledgements This work was supported by the National Natural Science Foundation of China （Grant No. 20533070）, and the Specialized Research Fund for the Doctoral Program of Higher Education （Grant No. 20050610039）.

摘　　要：By introducing the concept of spring energy of permanent dipole and taking the conforma-tions of solvent molecules into account,the formulas of electrostatic solvation energy in equilibrium and nonequilibrium are derived from the explicit solvent scheme,with the spatial distribution of the discrete permanent charges and induced dipoles of the sol-vent molecules involved. The energy change of sol-ute due to the variation of wave function from the case of vacuum to that in solution is estimated by treating the solvent effect as external field in the it-eration cycles of the self-consistent field. The ex-pression for spectral shift is deduced and applied to the processes of light absorption and emission in solution. According to the new formulations,the av-eraged solvent electrostatic potential/molecular dy-namics program is modified and adopted to investi-gate the equilibrium solvation energy of water mole-cule and spectral shift of acrolein.By introducing the concept of spring energy of permanent dipole and taking the conformations of solvent molecules into account, the formulas of electrostatic solvation energy in equilibrium and nonequilibrium are derived from the explicit solvent scheme, with the spatial distribution of the discrete permanent charges and induced dipoles of the solvent molecules involved. The energy change of solute due to the variation of wave function from the case of vacuum to that in solution is estimated by treating the solvent effect as external field in the iteration cycles of the self-consistent field. The expression for spectral shift is deduced and applied to ＇the processes of light absorption and emission in solution. According to the new formulations, the averaged solvent electrostatic potential/molecular dynamics program is modified and adopted to investigate the equilibrium solvation energy of water molecule and spectral shift of acrolein.

关 键 词：丙烯醛 分子动力学 溶剂模型 谱移 非平衡溶剂化 静电自由能 

分 类 号：O645.13[理学—物理化学]