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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Control of cis-Stilbene Photochemistry Using Shaped Ultraviolet Pulses
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Control of cis-Stilbene Photochemistry Using Shaped Ultraviolet Pulses

机译：使用成形紫外脉冲控制顺二苯乙烯光化学

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摘要

We demonstrate product branching control of the photoisomerization and cyclization reactions of cis-stilbene dissolved in n-hexane. An acousto-optical modulator-based pulse shaper was used at 266 nm, in a shaped pump-supercontinuum probe technique, to enhance and suppress the relative yields of the cis- to transstilbene isomerization as well as the cis-stilbene to 4a,4b-dihydrophenanthrene cyclization. Global, local,and single variable optimization control schemes were all successful at controlling stilbenes excited-state intramolecular rearrangements. The presence of multiphoton transitions was determined to be crucial in changing the yield under the experimental conditions employed. We have mapped experimental conditions in which multiphoton absorption was successful in controlling photoproduct branching ratios in stilbene, illustrated that the intensity dependence of the product yields can provide details of reactive channel branching ratios of higher excited-states, and shown that under the experimental conditions employed (150 fs laser) intensity control was the only mechanism available to the optimal control methods employed that could affect reaction yields.
机译：我们证明了顺式-苯乙烯溶解在正己烷中的光异构化和环化反应的产物分支控制。在整形泵超连续谱探针技术中，使用了基于声光调制器的脉冲整形器，波长为266 nm，以增强和抑制顺-向二苯乙烯异构化以及顺-苯乙烯向4a，4b-二氢菲环化。全局，局部和单变量优化控制方案都成功地控制了斯蒂苯类化合物的激发态分子内重排。在所采用的实验条件下，确定多光子跃迁的存在对于改变产率至关重要。我们绘制了实验条件，在该条件下多光子吸收成功地控制了二苯乙烯中的光产物分支比，说明了产物产率的强度依赖性可以提供更高激发态的反应性沟道分支比的细节，并表明在所采用的实验条件下（150 fs激光）强度控制是采用的可能影响反应产率的最佳控制方法的唯一机制。

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