Ab Initio Calculation of Homogeneous Outer Sphere Electron Transfer Rates: Application to M(OH2)63+/2+Redox Couples
Ab Initio Calculation of Homogeneous Outer Sphere Electron Transfer Rates: Application to M(OH2)63+/2+Redox Couples
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均匀外层电子转移率的从头计算：在 M(OH2)63 /2 氧化还原电对中的应用
DOI：
10.1021/jp994164h
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发表时间：
2000
影响因子：
2.9
通讯作者：
J. Rustad
中科院分区：
文献类型：
--
作者：
K. Rosso;J. Rustad
从头算密度泛函理论计算应用于预测背景电解质中一系列过渡金属六离子体的经典马库斯形式中的均匀外球电子转移速率。计算重组能量、频率因子、电子传输系数和有效电子传输距离。理论内球对重组能的贡献与根据实验自交换率估计的总重组能非常相关。由 Jahn-Teller 畸变产生的重要能量贡献被准确地包含在内球体项中。发现有效电子转移距离仅比平均计算的 M−O 距离之和稍长。计算的绝热自交换率与观察到的自交换率非常吻合。通过总能量差计算得出的双分子电子转移驱动力与...
Ab initio density functional theory calculations are applied to the prediction of homogeneous outer sphere electron transfer rates within the classical Marcus formalism for a series of transition metal hexaquo ions in a background electrolyte. Reorganization energies, frequency factors, electronic transmission coefficients, and the effective electron transfer distances are calculated. Theoretical inner sphere contributions to the reorganization energies correlate very well with total reorganization energies estimated from experimental self-exchange rates. Important energy contributions arising from Jahn−Teller distortions are accurately included in the inner sphere term. Effective electron transfer distances are found to be only slightly longer than the sum of the average calculated M−O distances. Calculated adiabatic self-exchange rates agree well with observed self-exchange rates. The driving force for bimolecular electron transfers, calculated from total energy differences, is found to compare well wit...