The theory of the Fe2+–Fe3+ electron exchange in water
The theory of the Fe2+–Fe3+ electron exchange in water
复制标题
水中Fe2+-Fe3+电子交换理论
DOI：
10.1063/1.443110
复制
发表时间：
1982
影响因子：
4.4
通讯作者：
M. Newton
中科院分区：
文献类型：
--
作者：
B. L. Tembe;H. Friedman;M. Newton
Fe2+ -Fe3 +电子交换的速率常数可表示为k23=∫0∞g23(r) k23(r) 4πr2 dr，该形式也可用于分析与Ni2+碰撞引起的Al3+核自旋弛豫数据。假设在这两种情况下平衡对相关函数g23(r)是离子组成和温度的相同函数，并且在自旋弛豫过程中，局部速率常数k23(r)具有可由Solomon-Bloembergen方程推导出来的形式。在交换反应的情况下，k23(r)理论是根据缓慢的内壳层或外壳层重组（激活）动力学的贡献而发展起来的。结论是，在目前的情况下，这些复杂因素并不重要，控制动力学是从反应物到产物的非绝热玻恩-奥本海默表面的交叉。如果碰撞中最小的金属-金属距离是g…
The rate constant for the Fe2+–Fe3+ electron exchange is formulated as k23= ∫ 0∞g23(r) k23(r) 4πr2 dr, a form which also is used to analyze the data for the nuclear spin relaxation in Al3+ induced by collision with Ni2+. It is assumed that the equilibrium pair correlation function g23(r) is the same function of ionic composition and temperature in the two cases and that in the spin relaxation process the local rate constant k23(r) has the form that may be deduced from the Solomon–Bloembergen equations. In the case of the exchange reaction the theory of k23(r) is developed with respect to the contributions from slow inner shell or outer shell reorganization (activation) dynamics. It is concluded that in the present case these complications are not important and that the controlling dynamics is the crossing from the reactant to the product diabatic Born– Oppenheimer surface. Neither the exchange nor the spin relaxation data can be accounted for if the smallest metal–metal distance in collisions is that g...