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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >O-2(-)center dot[Polar VOC] Complexes: H-Bonding versus Charge Dipole Interactions, and the Noninnocence of Formaldehyde
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O-2(-)center dot[Polar VOC] Complexes: H-Bonding versus Charge Dipole Interactions, and the Noninnocence of Formaldehyde

机译：O-2（ - ）中心点[Polar Voc]复合物：H键合与电荷偶极相互作用，以及甲醛的非营因素

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摘要

Anion photoelectron imaging was used to measure the photodetachment spectra of molecular complexes formed between O-2(-) and a range of atmospherically relevant polar molecules, including species with a carbonyl group (acetone, formaldehyde) and alcohols (ethanol, propenol, butenol). Experimental spectra are analyzed using a combination of Franck-Condon simulations and electronic structure calculations. Strong charge-dipole interactions and H-bonding stabilize the complex anions relative to the neutrals, resulting in a ca. 1 eV increase in electron binding energy relative to bare O-2(-), an effect more pronounced in complexes with H-bonding. In addition, broken degeneracy of the O-2-local pi g orbitals in the complexes results in the stabilization of the low-lying excited O-2 (a (1)Delta(g))center dot[polar VOC] state relative to the ground O-2 (X-3 Sigma(-)(g))center dot[polar VOC] state when compared to bare O-2. The spectra of the O-2(-)center dot[polar VOC] complexes exhibit less pronounced laser photoelectron angular distribution (PADs). The spectrum of O-2 formaldehyde is unique in terms of both spectral profile and PAD. On the basis of these experimental results in addition to computational results, the complex anion cannot be described as a distinct O-2 anion partnered with an innocent solvent molecule; the molecules are more strongly coupled through charge delocalization. Overall, the results underscore how the symmetry of the O-2 pi(g) orbitals is broken by different polar partners, which may have implications for atmospheric photochemistry and models of solar radiation absorption that include collision-induced absorption.
机译：Anion光电子成像用于测量在O-2（ - ）和一系列大气相关的极性分子之间形成的分子复合物的光透射光谱，包括具有羰基（丙酮，甲醛）和醇的物种（乙醇，丙烯醇，丁醇） 。使用Franck-Condon模拟和电子结构计算的组合分析实验光谱。强电荷 - 偶极相互作用和H键合相对于中性稳定复杂阴离子，导致CA. 1相对于裸O-2（ - ）的电子结合能量增加，效果在复合物中与H键合的效果更加明显。此外，复合物中O-2局部PI G轨道的破裂退化导致相对于的低洼激发O-2（A（1）Δ（g））中心点[极性VOC]状态的稳定性与裸O-2相比，地面O-2（x-3 sigma（ - ）（g））中心点[极化电源]状态。 O-2（ - ）中心点[极性VOC]复合物的光谱表现出较不明显的激光光电子角分布（焊盘）。 O-2甲醛的光谱在光谱曲线和垫方面是唯一的。在这些实验结果的基础上除了计算结果之外，复杂的阴离子不能描述为与无辜溶剂分子合作的不同O-2阴离子;分子通过电荷描移更强烈地耦合。总的来说，结果强调了O-2 PI（G）轨道的对称性由不同的极地伙伴打破，这可能对大气的光化学和太阳辐射吸收模型具有影响，包括碰撞诱导的吸收。

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