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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Nonstatistical Dissociation Dynamics of Nitroaromatic Chromophores
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Nonstatistical Dissociation Dynamics of Nitroaromatic Chromophores

机译：硝基芳族发育道的非统计解离动力学

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摘要

Organic carbon in the atmosphere is emitted from biogenic and anthropogenic sources and plays a key role in atmospheric chemistry, air quality, and climate. Recent studies have identified several of the major nitroaromatic chromophores embedded in organic "brown carbon" (BrC) aerosols. Indeed, nitroaromatic chromophores are responsible for the enhanced solar absorption of BrC aerosols, extending into the near UV (300-400 nm) and visible regions. Furthermore, BrC chromophores serve as temporary reservoirs of important oxidizing intermediates including hydroxyl (OH) and nitric oxide (NO) radicals that are released upon electronic excitation. The present work represents the first study of the 3SS nm photolysis of known BrC chromophores ortho-nitrophenol and 2-nitroresorcinol, as well as the prototypical nitroaromatic, nitrobenzene. Experiments are carried out in a pulsed supersonic jet expansion with velocity map imaging of NO X-2 Pi (nu '' = 0, J '') fragments to report on the photodissociation dynamics. The total kinetic energy release (TKER) distributions and the NO X-2 Pi (nu '' = 0, J '') product state distributions deviate significantly from Prior simulations, indicating that energy is partitioned nonstatistically following dissociation. Experiments are conducted in tandem with complementary calculations using multireference Moller-Plesset second-order perturbation theory (MRMPT2) for stationary points obtained by using multiconfiguration self-consistent field (MCSCF) with an aug-cc-pVDZ basis on the ground and lowest energy triplet electronic states. Furthermore, insights into the partitioning of energy upon photodissociation are achieved by using relaxed scans at the MCSCF/aug-cc-pVDZ level of theory. As a whole, the results suggest that upon excitation to S-1, all three nitroaromatics share a common overall mechanism for NO production involving isomerization of the nitro group, nonradiative relaxation to S-0, and dissociation to form rotationally hot NO.
机译：大气中的有机碳从生物生成和人为来源发出，在大气化学，空气质量和气候中起着关键作用。最近的研究已经确定了嵌入有机“棕色碳”（BRC）气溶胶中的几个主要的硝基芳族发色团。实际上，硝基芳族发色团负责增强BRC气溶胶的太阳能吸收，延伸到近UV（300-400nm）和可见区域。此外，BRC发色团作为临时储存器作为重要的氧化中间体，包括在电子激发时释放的羟基（OH）和一氧化氮（NO）基团。本作者代表了已知BRC发色团的3SS NM光解的第一研究，邻硝基苯酚和2-硝基丙烯醛，以及原型硝基芳族硝基苯。实验在脉冲超声波喷射膨胀中进行，具有NO X-2 PI（NU''= 0，J''）片段的速度映射成像，以报告光学解码动力学。总动能释放（TKER）分布和NO X-2 PI（NU''= 0，J'）产品状态分布显着地偏离了先前的模拟，表明能量在解离后不间断地划分。通过使用多重配置自一致性领域（MCSCF）在地面和最低能量三重态基础上使用多重配置自洽磁场（MCSCF）来串联进行互补计算的互补计算。电子国家。此外，通过在MCSCF / AUG-CC-PVDZ理论水平下使用松弛扫描，实现了在光度解放时能量划分的见解。总的来说，结果表明，在激发到S-1时，所有三种硝基甲瘤都具有涉及硝基群体的异构化的常见的总体机制，硝基对S-0的异构化，以及解离以形成旋转热的NO。

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