Pathway analysis of super-exchange electronic couplings in electron transfer reactions using a multi-configuration self-consistent field method.
Pathway analysis of super-exchange electronic couplings in electron transfer reactions using a multi-configuration self-consistent field method.
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使用多构型自洽场方法对电子转移反应中的超级交换电子耦合进行路径分析。
DOI：
10.1039/c0cp01051k
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
K. Ando
中科院分区：
文献类型：
--
作者：
H. Nishioka;K. Ando
利用多组态自洽场（MCSCF）计算的定域分子轨道，对电子转移反应中的超交换电子耦合进行了新的途径分析。在我们的分析中，电子耦合和隧道路径可以计算的配置相互作用（CI）的哈密顿矩阵从本地化MCSCF波函数。利用受限多活性空间（ORMAS）方法可以有效地生成施主、受主和中间构型状态函数（CSF）以及这些CSF之间的CI。为了将电子耦合表示为单个隧穿路径贡献的总和，我们采用了两种微扰方法：Löwdin投影迭代方法和高阶超交换方法。我们将它们应用于1，4-丁二醇和1，5-戊二醇的阴离子偶联反应。结果表明：（1）两种微扰方法计算的电子耦合与非微扰方法计算的电子耦合基本一致（基态和第一激发态之间的能量差的二分之一值），（2）主要隧穿途径由少量的低阶超交换途径组成，其中成键、反键或价外壳层轨道被使用一次或两次，大量高阶超交换通道间的相互干扰对整个电子耦合有显著贡献，而每一个通道的贡献都很小.我们的方法可以充分考虑非动力学电子关联和轨道弛豫的影响。通过与基于Koopmans定理（忽略两种效应）和基于冻结定域参考轨道的ORMAS-CI（忽略轨道弛豫效应）的分析比较，讨论了这些效应。
We present a novel pathway analysis of super-exchange electronic couplings in electron transfer reactions using localized molecular orbitals from multi-configuration self-consistent field (MCSCF) calculations. In our analysis, the electronic coupling and the tunneling pathways can be calculated in terms of the configuration interaction (CI) Hamiltonian matrix obtained from the localized MCSCF wave function. Making use of the occupation restricted multiple active spaces (ORMAS) method can effectively produce the donor, acceptor, and intermediate configuration state functions (CSFs) and CIs among these CSFs. In order to express the electronic coupling as a sum of individual tunneling pathways contributions, we employed two perturbative methods: Löwdin projection-iteration method and higher-order super-exchange method. We applied them to anion couplings of butane-1,4-diyl and pentane-1,5-diyl. The results were (1) the electronic couplings calculated from the two perturbative methods were in reasonable agreement with those from a non-perturbative method (one-half value of the energy difference between the ground and first excited states), (2) the main tunneling pathways consisted of a small number of lower-order super-exchange pathways where bonding, anti-bonding, or extra-valence-shell orbitals were used once or twice, and (3) the interference among a huge number of higher-order super-exchange pathways significantly contributed to the overall electronic coupling, whereas each of them contributed only fractionally. Our method can adequately take into account both effects of non-dynamical electron correlation and orbital relaxation. Comparing with the analyses based on the Koopmans' theorem (ignoring both effects) and the ORMAS-CIs from frozen localized reference orbitals (ignoring the effect of orbital relaxation), we discuss these effects.
影响因子：
18.3
作者：
Beratan, David N.;Skourtis, Spiros S.;Balabin, Ilya A.;Balaeff, Alexander;Keinan, Shahar;Venkatramani, Ravindra;Xiao, Dequan
通讯作者：
Xiao, Dequan
有效电子耦合和电荷转移态激发能的全电子计算：在 DNA pi 堆栈中空穴转移的应用。
DOI：
10.1063/1.3232007
发表时间：
2009
期刊：
The Journal of chemical physics
影响因子：
--
作者：
Migliore,Agostino
通讯作者：
Migliore,Agostino