Nonequilibrium Solvation Theory And Applications To Ultra-fast Processes

This dissertation consists of four parts. The first part includes chapter 1 and chapter 2. In this part, new expression of the nonequilibrium electrostatic free energy is established in the framework of continuous medium theory. The defects in the traditional theories are pointed out. The second part comprises chapter 3 and chapter 4. In this part, various models are deduced for the calculation of the solvent reorganization energy in electron transfer reactions and spectral shifts in solution. The numerical algorism of the nonequilibrium solvation energy is given for arbitrary solute cavity. In the third part, namely, Chapter 5, the new models are applied to the studies of the solvent reorganization energy and spectral shift. The last part (Chapter 6) gives the solvation energy for equilibrium and nonequilibrium by explicitly considering the structures and the interactions of solvent molecules. The formulas for calculating solvent reorganization energy and spectral shift are presented.From chapter 1 to chapter 4, this dissertation systematically introduces the new nonequilibrium solvation theory and models recently developed in our laboratory. The contributions of the candidate are as follows: the derivation of nonequilibrium electrostatic energy with interaction energy method, based on the rational energy decomposition, the analyses of the treatments by Cossi and Klamt in chapter 2, and the multipole expansion method, the derivation for solvent reorganization energy in single sphere model and the formulas for spectral shifts in two-sphere model (chapter 3). In chapter 5, I adopt some test calculations to verify the correctness of the new formulas and models. In Chapter 6, I present my important contribution to...