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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photodissociation of cyclobutyl bromide at 234 nm studied using velocity map imaging
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Photodissociation of cyclobutyl bromide at 234 nm studied using velocity map imaging

机译：速度图成像研究环丁基溴在234 nm处的光解离

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摘要

This study investigates the 234 nm photodissociation dynamics of cyclobutyl bromide using a two-dimensional photofragment velocity imaging technique. The spin-orbit ground- and excited-state Br(P-2) atoms are state-selectively detected via [2+1] resonance enhanced multiphoton ionization (REMPI), whereas the cyclobutyl radicals are ionized using 157 nm laser light. The Br(P-2(3/2)) and the Br(P-2(1/2)) atoms and their c-C4H7 radical cofragnients evidence a single-peaked, Gaussian-shaped translational energy distribution ranging from similar to 14 to similar to 39 kcal/mol and angular distributions with significant parallel character. The Br(P-2(1/2))/ Br(P-2(3/2)) spin-orbit branching ratio is determined to be 0.11 +/- 0.07 by momentum match between the Br(P-2) photofragments and the recoiling c-C4H7 fragments, assuming a uniform photoionization probability of the c-C4H7 radicals with an internal energy range of 10-35 kcal/mol. The REMPI line strength ratio for the detection of Br(P-2(3/2)) and Br(P-2(1/2)) atoms at 233.681 and 234.021 nm, respectively, is therefore derived to be 0.10 +/- 0.07. The measured recoil kinetic energies of the c-C4H7 radicals, and the resulting distribution of internal energies, indicates some of the radicals are formed with total internal energies above the barrier to isomerization and subsequent dissociation, but our analysis indicates they may be stable due to the substantial fraction of the internal energy which is partitioned to rotational energy of the radicals.
机译：本研究使用二维光碎速度成像技术研究了环丁基溴的234 nm光解离动力学。自旋轨道的基态和激发态Br（P-2）原子通过[2 + 1]共振增强多光子电离（REMPI）进行状态选择性检测，而环丁基自由基则使用157 nm激光进行电离。 Br（P-2（3/2））和Br（P-2（1/2））原子与它们的c-C4H7自由基共存证明单峰高斯形平移能分布范围从大约14类似于39 kcal / mol和具有明显平行特征的角度分布。通过Br（P-2）光片段之间的动量匹配将Br（P-2（1/2））/ Br（P-2（3/2））自旋轨道分支比确定为0.11 +/- 0.07并假设内部能量范围为10-35 kcal / mol的c-C4H7自由基具有均匀的光电离概率，并且卷曲c-C4H7片段。因此，分别用于检测233.681和234.021 nm处的Br（P-2（3/2））和Br（P-2（1/2））原子的REMPI线强度比推导为0.10 +/- 0.07。测得的c-C4H7自由基的反冲动能以及内部能量的分布表明，某些自由基是由总内部能量高于异构化和随后的离解能垒形成的，但我们的分析表明，由于内部能量的很大一部分分配给自由基的旋转能。

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