Short-time dynamics through conical intersections in macrosystems.
Short-time dynamics through conical intersections in macrosystems.
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DOI：
10.1007/978-94-007-2076-3_16
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发表时间：
2005-03
影响因子：
8.6
通讯作者：
L. Cederbaum;E. Gindensperger;I. Burghardt
中科院分区：
文献类型：
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作者：
L. Cederbaum;E. Gindensperger;I. Burghardt
我们提出了一种基于二次电子振动耦合（QVC）哈密顿量[New J Chem 17：7- 29，1993]和有效模形式主义[Phys Rev Lett 94：113003，2005]的方法，用于复杂分子系统中通过圆锥相交的短时动力学。在该方案中，整个系统的核自由度分为系统模式和环境模式。为了精确地描述宏观系统的短时动力学，只需要三个有效的环境模态和系统的模态。基于这种分解，在自相关函数的累积量展开中，精确的累积量被恢复到二阶。为了证明我们的方法的能力，并与其他结果进行比较，吡嗪分子被选为一个数值例子。
We present an approach based on the quadratic vibronic coupling (QVC) Hamiltonian [New J Chem 17:7–29,1993] and the effective-mode formalism [Phys Rev Lett 94:113003, 2005] for the short-time dynamics through conical intersections in complex molecular systems. Within this scheme the nuclear degrees of freedom of the whole system are split as system modes and as environment modes. To describe the short-time dynamics in the macrosystem precisely, only three effective environmental modes together with the system’s modes are needed. Based on this decomposition, in the cumulant expansion of the autocorrelation function, the exact cumulants are recovered up to the second order. To demonstrate the capability of our method and for comparison with other results, the pyrazine molecule is chosen as a numerical example.