A novel algorithm was designed and implemented to realize the numerical calculation of the solvent reorganization energy for electron transfer reactions, on the basis of nonequilibrium solvation theory and the dielect...A novel algorithm was designed and implemented to realize the numerical calculation of the solvent reorganization energy for electron transfer reactions, on the basis of nonequilibrium solvation theory and the dielectric polarizable continuum model. Applying the procedure to the well-investigated intramoleeular electron transfer in biphenyl-androstane-naphthyl and biphenyl-androstane-phenanthryl systems, the numerical results of solvent reorganization energy were determined to be around 60 k J/mol, in good agreement with experimental data. Koopman＇s theorem was adopted for the calculation of the electron transfer coupling element, associated with the linear reaction coordinate approximation. The values for this quantity obtained are acceptable when compared with experimental results.展开更多
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 spe...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.展开更多
As a successive work of our previous paper, 1 the electron transfer matrix element (V rp) in the oxidation of the simplified model molecule of α-amino carbon-centered radical by O 2 has been investigated wi...As a successive work of our previous paper, 1 the electron transfer matrix element (V rp) in the oxidation of the simplified model molecule of α-amino carbon-centered radical by O 2 has been investigated with ab initio calculation at the level of UHF/6-31++G**. Based on the optimized geometries of the reactant and the ion-pair complex obtained previously, the reaction heat and the inner reorganization energy have been obtained by constructing the potential energy curves of reactant and product states considering the solvent effect with the conductor-like screening model (COSMO). The solvent reorganization energy has been estimated using Lippert-Mataga relationship. The calculated results show that the value of V rp is several times larger than that of RT, which means that the model reaction is an adiabatic one. Theoretical investigation indicates that the solvent effect on the direct electron transfer (ET) process of oxidation of α-amino carbon-centered radical by oxygen is remarkable.展开更多
文摘A novel algorithm was designed and implemented to realize the numerical calculation of the solvent reorganization energy for electron transfer reactions, on the basis of nonequilibrium solvation theory and the dielectric polarizable continuum model. Applying the procedure to the well-investigated intramoleeular electron transfer in biphenyl-androstane-naphthyl and biphenyl-androstane-phenanthryl systems, the numerical results of solvent reorganization energy were determined to be around 60 k J/mol, in good agreement with experimental data. Koopman＇s theorem was adopted for the calculation of the electron transfer coupling element, associated with the linear reaction coordinate approximation. The values for this quantity obtained are acceptable when compared with experimental results.
基金ACKNOWLEDGMENTS This work was supported Science Foundation of China by the National Natural （No.91016002）.
文摘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.
文摘As a successive work of our previous paper, 1 the electron transfer matrix element (V rp) in the oxidation of the simplified model molecule of α-amino carbon-centered radical by O 2 has been investigated with ab initio calculation at the level of UHF/6-31++G**. Based on the optimized geometries of the reactant and the ion-pair complex obtained previously, the reaction heat and the inner reorganization energy have been obtained by constructing the potential energy curves of reactant and product states considering the solvent effect with the conductor-like screening model (COSMO). The solvent reorganization energy has been estimated using Lippert-Mataga relationship. The calculated results show that the value of V rp is several times larger than that of RT, which means that the model reaction is an adiabatic one. Theoretical investigation indicates that the solvent effect on the direct electron transfer (ET) process of oxidation of α-amino carbon-centered radical by oxygen is remarkable.
