Theoretical study of self-exchange electron-transfer reactions for the M(H2O)3.0.CO;2-J/asset/equation/tex2gif-ueqn-1.gif?v=1&t=h5o1nw4g&s=1376fb9f38de599480e9d63bb7cf311e3f6f276f" class="inlineGraphic"> (M = V, Cr, Mn, and Fe) systems

✍ Scribed by Dongju Zhang; Bingyou Zhuang; Dacheng Feng; Chengbu Liu

• Publisher: John Wiley and Sons
• Year: 2000
• Tongue: English
• Weight: 400 KB
• Volume: 78
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(2000)78:1<32::aid-qua5>3.0.co;2-j

✦ Synopsis

Based on an activation model, a available scheme to calculate the rate of the electron-transfer reaction between transition-metal complexes in aqueous solution is presented. Ab initio technique is used to determine the electron-transfer reactivity of the type M(H 2 O) 2+/3+ 6 of transition-metal complexes at the UMP2/6-311G level. The activation parameters and activation energies of the electron-transfer systems are obtained via the activation model. An alternative determining method of the potential energy surface (curve) slope at the crossing point is given in which the inner-sphere contribution of potential energy surface slope is expressed as the sum of two separate reactants. Theoretical self-exchange rate constants for M(H 2 O) 2+/3+ 6 (M = V, Cr, Mn, and Fe) systems are obtained at 298 K and zero ionic strength. The calculated results of the activation energy, electronic transmission factor, and electron-transfer rate are compared with the corresponding quasi-experimental values as well as those obtained from other methods, and better agreements are found. The present results indicate that the scheme can adequately describe the self-exchange reactions involved in this study.