After the electron transfers from the metal electrode to the Fe3+(H2O)(6) ion, the free energy of activation of this electron transfer reaction is calculated, then using the transition probability which is calculated ...After the electron transfers from the metal electrode to the Fe3+(H2O)(6) ion, the free energy of activation of this electron transfer reaction is calculated, then using the transition probability which is calculated by the perturbed degeneration theory and the Fermi golden rule,, the rate constant is gotten. Compared with the experimental results, it is satisfactory.展开更多
he electrochemistry of cytochrome C was investigated at a spectrographicgraphite electrode. In phosphate buffer solution (pH= 7. 0) , cytochrome C showedstable and quasi-reversible response. The formal potential E￣(o...he electrochemistry of cytochrome C was investigated at a spectrographicgraphite electrode. In phosphate buffer solution (pH= 7. 0) , cytochrome C showedstable and quasi-reversible response. The formal potential E￣(o') was 0. 015 V (at25℃ , vs. SCE) and the heterogeneous electron transfer rate constant k_s obtainedvaried form 1. 10×10￣(-3) cm · s￣(-1) to 1. 80k×10￣(-3) cm · s￣(-1). The thermodynamic pa-rameters of the electron transfer reaction of cvtochrome C was also estimated. Fur-thermore, the effect of the various electrode surface states on the electrochemistryof cytochrome C was discussed.展开更多
Electron transfer (ET) reactions are of great importance to nearly every subdiscipline of chemistry. Marcus classical model, quantum model treating the nuclei as a quantum system, and the semiclassical model neglectin...Electron transfer (ET) reactions are of great importance to nearly every subdiscipline of chemistry. Marcus classical model, quantum model treating the nuclei as a quantum system, and the semiclassical model neglecting the nuclear tunneling effects but taking the nonadiabatic transition between two electronic states into account, have been widely used in the kinetic research of ET reactions. For the symmetric double-well potential vs. the nuclear configuration Q along the reaction path (fig.1(a)), a semiclassical kinetic model展开更多
2,3,5,6-Tetrachloride-quinone was anchored to a gold surfare through the self-assem-bled monolayers of dithiol [DT HS-(CH2).-SH n=2,4,6,8,10]. The surface coverage of the anchoredTQ was esteminated to be 4.0 ×10-...2,3,5,6-Tetrachloride-quinone was anchored to a gold surfare through the self-assem-bled monolayers of dithiol [DT HS-(CH2).-SH n=2,4,6,8,10]. The surface coverage of the anchoredTQ was esteminated to be 4.0 ×10-11 mol’cm-2. The electron transfer rate constant Ket associatedwith the redox process of anchored film decreased from 6.75 s-1 at n=2 to 0.169 s-1 at n=10 withincreasing the chain length of the DT SAMs througth the redox potential of TQ. The turnningbarrier conefficient.(β) of the electron transfer was estimated to be 0.82A-1 from the observed linearrelationship between the Ket and the monolayer chain length.展开更多
文摘After the electron transfers from the metal electrode to the Fe3+(H2O)(6) ion, the free energy of activation of this electron transfer reaction is calculated, then using the transition probability which is calculated by the perturbed degeneration theory and the Fermi golden rule,, the rate constant is gotten. Compared with the experimental results, it is satisfactory.
文摘he electrochemistry of cytochrome C was investigated at a spectrographicgraphite electrode. In phosphate buffer solution (pH= 7. 0) , cytochrome C showedstable and quasi-reversible response. The formal potential E￣(o') was 0. 015 V (at25℃ , vs. SCE) and the heterogeneous electron transfer rate constant k_s obtainedvaried form 1. 10×10￣(-3) cm · s￣(-1) to 1. 80k×10￣(-3) cm · s￣(-1). The thermodynamic pa-rameters of the electron transfer reaction of cvtochrome C was also estimated. Fur-thermore, the effect of the various electrode surface states on the electrochemistryof cytochrome C was discussed.
基金Project supported by the National Natural Science Foundation of China.
文摘Electron transfer (ET) reactions are of great importance to nearly every subdiscipline of chemistry. Marcus classical model, quantum model treating the nuclei as a quantum system, and the semiclassical model neglecting the nuclear tunneling effects but taking the nonadiabatic transition between two electronic states into account, have been widely used in the kinetic research of ET reactions. For the symmetric double-well potential vs. the nuclear configuration Q along the reaction path (fig.1(a)), a semiclassical kinetic model
文摘2,3,5,6-Tetrachloride-quinone was anchored to a gold surfare through the self-assem-bled monolayers of dithiol [DT HS-(CH2).-SH n=2,4,6,8,10]. The surface coverage of the anchoredTQ was esteminated to be 4.0 ×10-11 mol’cm-2. The electron transfer rate constant Ket associatedwith the redox process of anchored film decreased from 6.75 s-1 at n=2 to 0.169 s-1 at n=10 withincreasing the chain length of the DT SAMs througth the redox potential of TQ. The turnningbarrier conefficient.(β) of the electron transfer was estimated to be 0.82A-1 from the observed linearrelationship between the Ket and the monolayer chain length.
