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首页> 外文期刊>Physical chemistry chemical physics: PCCP >Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate
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Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate

机译：通往漫游的道路。三重碎裂和圆锥形交叉在光化学反应中的作用：甲酸甲酯的实验和理论

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The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged "reactivity funnel" of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states.
机译：探索具有足够能量以产生不同产物的分子的替代道路可以预测并最终控制化学反应的结果。用于监视激光诱导的光解离的先进成像技术在这里与动力学仿真相结合，涉及在量子化学势能表面上生成的大量经典轨迹集。甲酸甲酯HCOOCH3以接近三重碎裂阈值的能量被光解为H，CO和OCH3。 CO的速度和旋转分布的图像显示出替代路线的特征，例如最近指定为过渡状态与漫游介导的路线。此外，给出了三重碎裂途径的证明，并且还通过中间HCO自由基的H原子产物成像和FTIR时间分辨光谱证实。另外，通过圆锥形相交所促进的非绝热跃迁的相关性通过模拟被澄清为有机光化学的特权“反应漏斗”，从而分子光激发的结果被传递到电子基态。

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