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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ab initio characterization of electron transfer coupling in photoinduced systems: Generalized Mulliken-Hush with configuration-interaction singles
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Ab initio characterization of electron transfer coupling in photoinduced systems: Generalized Mulliken-Hush with configuration-interaction singles

机译：光诱导系统中电子转移耦合的从头算表征：具有构型相互作用单分子的广义Mulliken-Hush

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摘要

To calculate electronic couplings for photoinduced electron transfer (ET) reactions, we propose and test the use of ab initio quantum chemistry calculation for excited states with the generalized Mulliken-Hush (GMH) method. Configuration-interaction singles (CIS) is proposed to model the locally excited (LE) and charge-transfer (CT) states. When the CT state couples with other high lying LE states, affecting coupling values, the image charge approximation (ICA), as a simple solvent model, can lower the energy of the CT state and decouple the undesired high-lying local excitations. We found that coupling strength is weakly dependent on many details of the solvent model, indicating the validity of the Condon approximation. Therefore, a trustworthy value can be obtained via this CIS-GMH scheme, with ICA used as a tool to improve and monitor the quality of the results. Systems we tested included a series of rigid, sigma-linked donor-bridge-acceptor compounds where "through-bond" coupling has been previously investigated, and a pair of molecules where "through-space" coupling was experimentally demonstrated. The calculated results agree well with experimentally inferred values in the coupling magnitudes (for both systems studied) and in the exponential distance dependence (for the through-bond series). Our results indicate that this new scheme can properly account for ET coupling arising from both through-bond and through-space mechanisms.
机译：为了计算光致电子转移（ET）反应的电子耦合，我们提出并测试了用广义Mulliken-Hush（GMH）方法从头算量子化学计算激发态的方法。提出了配置相互作用单（CIS）来模拟局部激发（LE）和电荷转移（CT）状态。当CT状态与其他处于高位的LE状态耦合并影响耦合值时，作为简单溶剂模型的图像电荷近似值（ICA）可以降低CT状态的能量，并消除不希望的高局部激发。我们发现，耦合强度几乎不依赖于溶剂模型的许多细节，这表明了Condon逼近的有效性。因此，通过这种CIS-GMH方案可以获得可信赖的价值，而ICA被用作改善和监测结果质量的工具。我们测试的系统包括一系列刚性的，与sigma相连的供体-桥-受体化合物，其中先前已研究过“贯穿键”耦合，而一对分子则通过实验证明了“贯穿空间”耦合。计算结果与耦合大小（对于所研究的两个系统）和指数距离相关性（对于键合序列）的实验推断值非常吻合。我们的结果表明，该新方案可以适当地考虑通过键合和空间机制引起的ET耦合。

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