Deconstructing field-induced ketene isomerization through Lagrangian descriptors.
Deconstructing field-induced ketene isomerization through Lagrangian descriptors.
复制标题
通过拉格朗日描述符解构场诱导的乙烯酮异构化。
DOI：
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
R. Hernandez
中科院分区：
文献类型：
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作者：
G. Craven;R. Hernandez
利用拉格朗日描述子的方法，构造了场致异构化中态转变的含时几何分离矩阵。得到了时变过渡态的稳定流形和不稳定流形，得到了在振荡电场作用下，作为控制构型变化的动态相空间对象的时变过渡态流形。通过对Gezelter-Miller势能面的经典轨迹研究和与含时电场耦合的近似偶极矩模型，对异构化反应动力学进行了模拟。我们通过将初始相空间划分为根据在给定时间达到的产物状态来标记的盆地，获得了在不同场强和振荡频率下反应几何的表示。这些盆地之间的边界与使用拉格朗日描述符获得的边界是一致的，即使在呈现混沌动力学的区域也是如此。这项工作的主要成果是：验证和推广了由拉格朗日描述符建立的过渡态理论框架，阐述了该理论对周期性和非周期性驱动的分子体系的适用性，并预测了利用外场控制烯酮及其衍生物异构化的区域。
The time-dependent geometrical separatrices governing state transitions in field-induced ketene isomerization are constructed using the method of Lagrangian descriptors. We obtain the stable and unstable manifolds of time-varying transition states as dynamic phase space objects governing configurational changes when the ketene molecule is subjected to an oscillating electric field. The dynamics of the isomerization reaction are modeled through classical trajectory studies on the Gezelter-Miller potential energy surface and an approximate dipole moment model which is coupled to a time-dependent electric field. We obtain a representation of the reaction geometry, over varying field strengths and oscillation frequencies, by partitioning an initial phase space into basins labeled according to which product state is reached at a given time. The borders between these basins are in agreement with those obtained using Lagrangian descriptors, even in regimes exhibiting chaotic dynamics. Major outcomes of this work are: validation and extension of a transition state theory framework built from Lagrangian descriptors, elaboration of the applicability for this theory to periodically- and aperiodically-driven molecular systems, and prediction of regimes in which isomerization of ketene and its derivatives may be controlled using an external field.
影响因子：
2.4
作者：
Boland, Richard P.;Galla, Tobias;McKane, Alan J.
通讯作者：
McKane, Alan J.
蛋白质折叠动力学的周期性和随机热调节。
DOI：
10.1063/1.4887360
发表时间：
2014
期刊：
The Journal of chemical physics
影响因子：
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作者：
Platkov,Max;Gruebele,Martin
通讯作者：
Gruebele,Martin