Aspects of aqueous iron and manganese (II/III) self-exchange electron transfer reactions
Aspects of aqueous iron and manganese (II/III) self-exchange electron transfer reactions
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铁和锰水溶液 (II/III) 自交换电子转移反应的方面
DOI：
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发表时间：
2004
期刊：
影响因子：
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通讯作者：
M. Dupuis
中科院分区：
文献类型：
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作者：
K. Rosso;Dayle M. Smith;M. Dupuis
用从头算方法计算了外层Fe（OH 2）6 II/III和Mn（OH 2）6 II/III自交换电子转移反应的重组能λ和电子耦合矩阵元VAB.对于Fe的情况下，我们发现一个明显的影响VAB取决于少数自旋电子是否占据的dxy轨道或混合物的dxz/dyz轨道的Fe II离子。虽然这两种可能的近似等能电子接受态改变了VAB的大小和距离依赖性，但它们不会对内部重组能λI产生任何显著影响。VAB的幅度和距离的依赖性被发现是强烈依赖于遇到的方向，正如预期的那样。角到角相遇方向的VAB值在任何给定的ET距离下都比面对面相遇方向的VAB值大得多。衰减参数β的值与公认的值非常一致。绝热性准则与……
Ab initio methods were applied to the calculation of the reorganization energy λ and the electronic coupling matrix element VAB for the outer-sphere Fe(OH2)6II/III and Mn(OH2)6II/III self-exchange electron transfer (ET) reactions. For the Fe case, we find an appreciable effect on VAB depending on whether the minority spin electron occupies the dxy orbital or a mixture of dxz/dyz orbitals in the FeII ion. While these two possible nearly isoenergetic electron accepting states alter the magnitude and distance dependence of VAB, they do not affect the internal reorganization energy λI to any significant level. The magnitude and distance dependence of VAB are found to be strongly dependent on encounter orientation, as expected. VAB values for corner-to-corner encounter orientations are substantially larger at any given ET distance considered than those for face-to-face encounter orientations. Values of the decay parameter β are in good agreement with well-accepted values. The adiabaticity criterion is tied to ...