A Straightforward Method of Analysis for Direct Quantum Dynamics: Application to the Photochemistry of a Model Cyanine
A Straightforward Method of Analysis for Direct Quantum Dynamics: Application to the Photochemistry of a Model Cyanine
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DOI：
10.1021/jp101574b
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发表时间：
2010-08-26
影响因子：
2.9
通讯作者：
Robb, Michael A.
中科院分区：
文献类型：
--
作者：
Allan, Charlotte S. M.;Lasorne, Benjamin;Robb, Michael A.
我们提出了一种新的基于mulliken型总体分析的直接量子动力学模拟分析方法。这提供了对波包的直接解释，其方式与通常分析半经典轨迹的方式大致相同，结果可以看作是一组耦合的量子轨迹。我们将此应用于12原子模型菁氨酸的光化学研究，以探索智能最优控制的可能性。本文提出的工作建立在以前的半经典动力学模拟的基础上[Hunt， P. a .；罗柏，M. A . J .化学。这些计算表明，通过控制初始波包中动量分量的分布，应该有可能将系统驱动到锥形相交缝的特定区域，并最终控制产品分布。最优控制方法在实验中证实了这一点[Dietzek， B；Bruggemann， B, Pascher， T；亚采夫，a.j. Ant。化学。本文的目的是在量子动力学背景下证明这一点，并进一步深入了解控制所需的条件。我们的结果表明，直接处理跨顺扭模是无效的。相反，人们需要减少骨骼变形坐标中的动量，以在大扭转角的最小圆锥相交附近促使无辐射衰变。
We present in a new way of analyzing direct quantum dynamics simulations based on a Mulliken-type population analysis. This provides a straightforward interpretation of the wavepacket in much the same way as semiclassical trajectories are usually analyzed The result can be seen as a coupled set of quantum trajectories. We apply this to the study of the photochemistry of a 12-atom model cyanine to explore possibilities for intelligent optimal control The work presented here builds on previous semiclassical dynamics simulations [Hunt, P. A.; Robb, M. A J Am Chem. Soc. 2005 127, 5720] Those calculations suggested that, by controlling the distribution of momentum components in the initial wavepacket, it should be possible to drive the system to a specific region of the conical intersection seam and ultimately control the product distribution. This was confirmed experimentally by optimal control methods [Dietzek, B; Bruggemann, B, Pascher, T; Yartsev, A.J Ant. Chem. Soc 2007 129, 13014] This paper aims to demonstrate this in a quantum dynamics context and give further insight into the conditions required for control Our results show that directly addressing the trans-cis torsional modes is not efficient. Instead, one needs to decrease the momentum in the skeletal deformation coordinates to prompt radiationless decay near the minimum conical intersection at large twist angles.