Inelastic Charge Transfer Dynamics in Donor-Bridge-Acceptor Systems Using Optimal Modes
Inelastic Charge Transfer Dynamics in Donor-Bridge-Acceptor Systems Using Optimal Modes
复制标题
使用最佳模式的供体-桥-受体系统中的非弹性电荷转移动力学
DOI：
10.1002/9781119374978.ch6
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
E. Bittner
中科院分区：
文献类型：
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作者：
Xummo Yang;E. Bittner
我们提出了一种新颖的{\em ab initio}方法，用于基于投影算子方案计算分子内电荷和能量转移率，该方案解析出伴随电子跃迁的特定内部核运动。我们的方法将电子和核自由度之间的耦合集中到少量的简化谐波模式中，这些谐波模式可以写成分子系统关于给定电子最小值的振动简正模式的线性组合。使用无时间卷积主方程方法，通过精确的量子化学方法参数化，我们将该方法与实验结果和马库斯理论的预测进行基准测试，以实现一系列供体-桥-受体系统的三重态能量转移。我们发现，仅使用一种简化模式（称为“主”模式），就可以获得对黄金法则速率常数的准确评估，并深入了解负责耦合初始和最终电子态的核运动。我们通过计算模型供体-桥-受体复合体中的非弹性电子跃迁速率来证明该方法的实用性，该复合体已通过实验表明其激子转移路径可以通过其振动模式的模式特异性红外激发来彻底改变。
We present a novel {\em ab initio} approach for computing intramolecular charge and energy transfer rates based upon a projection operator scheme that parses out specific internal nuclear motions that accompany the electronic transition. Our approach concentrates the coupling between the electronic and nuclear degrees of freedom into a small number of reduced harmonic modes that can be written as linear combinations of the vibrational normal modes of the molecular system about a given electronic minima. Using a time-convolutionless master-equation approach, parameterized by accurate quantum-chemical methods, we benchmark the approach against experimental results and predictions from Marcus theory for triplet energy transfer for a series of donor-bridge-acceptor systems. We find that using only a single reduced mode--termed the "primary" mode, one obtains an accurate evaluation of the golden-rule rate constant and insight into the nuclear motions responsible for coupling the initial and final electronic states. We demonstrate the utility of the approach by computing the inelastic electronic transition rates in a model donor-bridge-acceptor complex that has been experimentally shown that its exciton transfer pathway can be radically modified by mode-specific infrared excitation of its vibrational mode.
影响因子：
56.9
作者：
Leyun Zhu;J. Sage;P. Champion
通讯作者：
Leyun Zhu;J. Sage;P. Champion
影响因子：
16.6
作者：
通讯作者：
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