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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Microscopic Based Density Matrix Treatments of Electron-Transfer Reactions in Condensed Phases
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Microscopic Based Density Matrix Treatments of Electron-Transfer Reactions in Condensed Phases

机译：缩合相中电子转移反应的微观基密度矩阵处理

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Several non-phenomenological density matrix treatments of electron-transfer (ET) reactions in condensed phases are developed and examined. The methods consider the donor and acceptor system (the solute) under the influence of the surrounding fluctuating solvent. The main emphasis is placed on semiclassical methods, where the starting point is the Hamiltonian of the quantum mechanical electronic states of the solute. The diagonal elements of the Hamiltonian include the fluctuations of the solute electronic energies as a result of the interaction between the solute and the field from the classically moving solvent molecules. The fluctuating Hamiltonian is used to construct a Liouville equation, which is treated by three approaches. The first method is based on a direct numerical integration of the relevant Liouville equation. The second involves the use of a second-order Liouville equation, and the third involves the use of a Redfield type equation. The methods are examined by simulating electron transfer between two sodium-like atoms that are held at a 4 A separation in water. The simulations generate the fluctuations of the electronic energies of the states that are involved in the electron-transfer process. The fluctuation energies are then used in evaluating the rate constant of the reaction as a function of its assumed free energies. The results of the three approaches are similar to the corresponding results obtained from the Marcus equation. However, the Redfield equation converges much more quickly than the direct Liouville equation and its second-order version. The problems associated with the semiclassical treatments are briefly considered, emphasizing the approximation involved in treating the solvent motion classically. Some of these problems can be overcome by a previously developed density matrix approach~1 that uses classical simulations to evaluate the Franck-Condon factors of the solvent vibronic states. This vibronic density matrix treatment is briefly described and used in simulating an electron-transfer reaction in the reaction center from Rps. viridis.
机译：凝结相中电子转移（ET）反应的几种非现象学密度矩阵处理方法得到了发展和研究。该方法在周围波动的溶剂的影响下考虑了供体和受体系统（溶质）。主要重点放在半经典方法上，其中起点是溶质的量子力学电子态的哈密顿量。哈密​​顿量的对角元素包括溶质电子能量的波动，这是溶质与经典运动溶剂分子的电场之间相互作用的结果。波动的哈密顿量用于构造一个Liouville方程，可以通过三种方法对其进行处理。第一种方法基于相关Liouville方程的直接数值积分。第二个涉及使用二阶Liouville方程，第三个涉及使用Redfield型方程。通过模拟在水中保持4 A分离的两个钠样原子之间的电子转移来检验这些方法。模拟产生电子转移过程中所涉及的状态的电子能量的波动。然后，将波动能用于根据其假定的自由能来评估反应的速率常数。三种方法的结果与从Marcus方程获得的相应结果相似。但是，Redfield方程的收敛速度比直接Liouville方程及其二阶方程快得多。简要考虑了与半经典处理相关的问题，强调了经典地处理溶剂运动所涉及的近似值。这些问题中的一些可以通过使用经典模拟评估溶剂振动状态的弗兰克-康登因子的先前开发的密度矩阵方法来克服。简要描述了这种振动密度矩阵处理，并将其用于模拟Rps在反应中心中的电子转移反应。绿色。

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