Allene and pentatetraene cations as models for intramolecular charge transfer: vibronic coupling Hamiltonian and conical intersections.
Allene and pentatetraene cations as models for intramolecular charge transfer: vibronic coupling Hamiltonian and conical intersections.
复制标题
丙二烯和五四烯阳离子作为分子内电荷转移的模型：振动耦合哈密顿和圆锥形交叉。
DOI：
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发表时间：
2005
影响因子：
4.4
通讯作者：
L. Cederbaum
中科院分区：
文献类型：
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作者：
Andreas Markmann;G. Worth;L. Cederbaum
我们考虑涉及简并组分的阳离子态的电子振动耦合效应，这些简并组分可以表示为位于短积聚烯分子丙二烯和五四烯两端的电荷。我们的目标是动态模拟一个组件被人为减少时的电荷转移过程。我们对这些态内的 Jahn-Teller 电子振动相互作用以及它们与一些邻近态的伪 Jahn-Teller 耦合进行建模。对于这些状态的流形，我们计算了沿所有核自由度的从头算绝热势能表面的横截面，包括距平衡较远的点，以增加我们模型的物理意义。丙二烯和五四烯的阳离子态的从头算基于四阶Møller-Plesset方法和外价格林函数方法。在某些情况下，我们必须超越这种方法，并使用更复杂的三阶代数图解构造方法来包含与卫星状态的交集。五态、全模式非绝热振动耦合模型哈密顿量的参数是对这些势进行最小二乘拟合的。非绝热模型哈密顿量的耦合参数使得与丙二烯相比，预计五四烯对间接电荷转移的偏好增强。
We consider the vibronic coupling effects involving cationic states with degenerate components that can be represented as charge localized at either end of the short cumulene molecules allene and pentatetraene. Our aim is to simulate dynamically the charge transfer process when one component is artificially depopulated. We model the Jahn-Teller vibronic interaction within these states as well as their pseudo-Jahn-Teller coupling with some neighboring states. For the manifold of these states, we have calculated cross sections of the ab initio adiabatic potential energy surfaces along all nuclear degrees of freedom, including points at large distances from the equilibrium to increase the physical significance of our model. Ab initio calculations for the cationic states of allene and pentatetraene were based on the fourth-order Møller-Plesset method and the outer valence Green's function method. In some cases we had to go beyond this method and use the more involved third-order algebraic diagrammatic construction method to include intersections with satellite states. The parameters for a five-state, all-mode diabatic vibronic coupling model Hamiltonian were least-square fitted to these potentials. The coupling parameters for the diabatic model Hamiltonian are such that, in comparison to allene, an enhanced preference for indirect charge transfer is predicted for pentatetraene.