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 deri...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.展开更多
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）.
文摘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.
