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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Photodissociation Dynamics of Benzoyl Chloride at 235 nm: Resonance-Enhanced Multiphoton Ionization Detection of Cl and HCl
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Photodissociation Dynamics of Benzoyl Chloride at 235 nm: Resonance-Enhanced Multiphoton Ionization Detection of Cl and HCl

机译：苯甲酰氯在235 nm处的光解离动力学：Cl和HCl的共振增强多光子电离检测

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摘要

The photodissociation dynamics of benzoyl chloride at 235 nm has been investigated and compared with that of 2-furoyl chloride. Atomic Cl and molecular HCl channels have been detected in benzoyl chloride by employing resonance-enhanced multiphoton ionization technique and time-of-flight mass spectrometry. Both the Cl fragments, Cl(~2P_(J=3/2), relative quantum yield 0.70 ± 0.15) and Cl*(~2P_(J=1/2)), show isotropic angular distribution and bimodal translational energy distributions. The predominant high kinetic energy channel contributes 72% to the C?Cl bond scission and arises from the S_1 state having nπ* character of benzoyl chloride. However, the low-energy Cl and HCl channels originate from the ground electronic state. The most plausible mechanism of HCl formation is proposed based on molecular orbital calculations. In contrast to benzoyl chloride, the HCl channel is not observed in 2-furoyl chloride on excitation at 235 nm, and this is attributed to an energy constraint.
机译：研究了苯甲酰氯在235 nm处的光解离动力学，并将其与2-糠酰氯进行了光解离。通过采用共振增强的多光子电离技术和飞行时间质谱，已在苯甲酰氯中检测到了原子Cl和HCl通道。 Cl片段Cl（〜2P_（J = 3/2），相对量子产率0.70±0.15）和Cl *（〜2P_（J = 1/2））均表现出各向同性的角度分布和双峰平移能量分布。主要的高动能通道对C 2 Cl键的断裂有72％的贡献，并来自具有苯甲酰氯的nπ*特征的S_1状态。但是，低能Cl和HCl通道起源于基态电子状态。根据分子轨道计算，提出了最合理的HCl形成机理。与苯甲酰氯相反，在235 nm激发下在2-糠酰氯中未观察到HCl通道，这归因于能量限制。

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