All mode dynamics at the conical intersection of an octa-atomic molecule: Multi-configuration time-dependent Hartree (MCTDH) investigation on the butatriene cation
All mode dynamics at the conical intersection of an octa-atomic molecule: Multi-configuration time-dependent Hartree (MCTDH) investigation on the butatriene cation
复制标题
八原子分子圆锥形交叉处的所有模式动力学：丁三烯阳离子的多构型时间依赖性 Hartree (MCTDH) 研究
DOI：
10.1063/1.1384872
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发表时间：
2001
影响因子：
4.4
通讯作者：
L. Cederbaum
中科院分区：
文献类型：
--
作者：
Chr. Cattarius;G. Worth;H. Meyer;L. Cederbaum
八原子丁三烯阳离子（C4 H4+）的基态和第一激发电子态呈现多维圆锥相交。这个交叉点在能量上是低的，并且位于中性分子基态的弗兰克-康登区域附近。因此，圆锥形的交叉点主导了该分子电离过程中的核动力学。这是一个特别有趣的电子振动耦合的例子，在能谱中引入了一个新的结构化带。在这项工作中，势能面和他们的相交的从头计算方法进行了研究。一个非绝热模型哈密顿量，包括所有可能的线性，二次和双线性振动耦合项的介绍，与耦合常数确定的从头算数据拟合。所有18个振动模式的核动力学，然后通过使用多组态含时Hartree方法传播波包进行评估。最后，光电…
The ground state and the first excited electronic states of the octa-atomic butatriene cation (C4H4+) exhibit a multidimensional conical intersection. This intersection is energetically low lying and is located in the vicinity of the Franck–Condon region of the neutral molecule’s ground state. The conical intersection thus dominates the nuclear dynamics in ionization processes of this molecule. This is a particularly interesting example of vibronic coupling, introducing what appears to be a new, structured band into the energy spectrum. In this work, the potential energy surfaces and their intersection are investigated by ab initio methods. A diabatic model Hamiltonian including all possible linear, quadratic and bilinear vibronic coupling terms is introduced, with coupling constants determined by a fit to the ab initio data. The nuclear dynamics of all 18 vibrational modes is then evaluated by propagating the wave packet using the multi-configuration time-dependent Hartree method. Finally, the photoelect...