Collision dynamics and reactive uptake of OH radicals at liquid surfaces of atmospheric interest.
Collision dynamics and reactive uptake of OH radicals at liquid surfaces of atmospheric interest.
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大气感兴趣的液体表面的碰撞动力学和 OH 自由基的反应吸收。
DOI：
10.1039/c0cp02734k
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
Waring C
中科院分区：
文献类型：
--
作者：
Waring C
OH自由基从一系列潜在反应性有机液体表面的非弹性散射：角鲨烷（C30 H62，2，6，10，15，19，23-六甲基二十四烷）;角鲨烯（C30 H50，反式-2，6，10，15，19，23-六甲基二十四碳-2，6，10，14，18，22-六烯）和油酸（C18 H34 O2，顺式-9-十八烷酸）。将液体长链全氟化聚醚（PFPE，Krytox® 1506）作为化学惰性参比物进行比较。气相OH的平均实验室框架动能为54 kJ mol−1，是由低压HONO在液面上方短距离（9 mm）处的355 nm光解产生的。通过激光诱导荧光（LIF）在相同距离处检测到散射OH。在选定的OHv′ = 0，N′旋转水平下，记录了作为光解探针延迟函数的外观曲线。动量转移到表面的效率是最低的PFPE和最高的角鲨烷，与角鲨烯和油酸的中间体，但在所有情况下的速度分布明显太热，是一致的热适应机制。发现旋转分布是散射OH速度的函数。对于N′ = 1和5的相对通量所暗示的通常高的旋转温度由每种液体的轮廓的峰值处的LIF激发光谱证实。平移到旋转能量转移的趋势与从平移无弹性推断的表面刚度序列大致一致。由HONO光解产生的OH精细结构和Λ-双重态的非统计分布似乎在与液体表面的碰撞中被有效地完全扰乱。考虑到产物的旋转分布，并假设100%的OH从PFPE散射，积分OH存活概率为：角鲨烷（0.70 ± 0.08），角鲨烯（0.61 ± 0.07）和油酸（0.76 ± 0.10）。“缺失的”OH被认为在液体表面发生了反应。详细的外观配置文件的比较表明，角鲨烷和角鲨烯之间的主要区别是缓慢移动的OH的损失，在乙烯基网站的额外的捕获机制一致。
The inelastic scattering of OH radicals from the surfaces of a sequence of potentially reactive organic liquids: squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane); squalene (C30H50, trans-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene); and oleic acid (C18H34O2, cis-9-octadecanoic acid) was studied experimentally. A liquid long-chain perfluorinated polyether (PFPE, Krytox® 1506) was compared as a chemically inert reference. Gas-phase OH with an average laboratory-frame kinetic energy of 54 kJ mol−1 was generated by 355-nm photolysis of a low-pressure of HONO a short distance (9 mm) above the liquid surface. Scattered OH was detected at the same distance by laser-induced fluorescence (LIF). Appearance profiles as a function of photolysis-probe delay were recorded for selected OHv′ = 0, N′ rotational levels. The efficiency of momentum transfer to the surface is least for PFPE and highest for squalane, with squalene and oleic acid intermediate, but in all cases the speed distributions are markedly too hot to be consistent with a thermal accommodation mechanism. The rotational distribution is found to be a function of scattered OH speed. The generally high rotational temperatures implied by the relative fluxes for N′ = 1 and 5 were confirmed by LIF excitation spectra at the peak of the profile for each liquid. The trends in translational-to-rotational energy transfer were broadly consistent with the sequence in surface stiffness inferred from the translational inelasticity. The non-statistical distribution of OH fine-structure and Λ-doublet states produced by HONO photolysis appears to be effectively completely scrambled in collisions with the liquid surfaces. With due account taken of the product rotational distributions, and assuming that 100% of the OH scatters from PFPE, the integrated OH survival probabilities were: squalane (0.70 ± 0.08), squalene (0.61 ± 0.07) and oleic acid (0.76 ± 0.10). The ‘missing’ OH is presumed to have reacted at the liquid surface. Detailed comparison of the appearance profiles suggests that the main difference between squalane and squalene is loss of slower-moving OH, consistent with an additional capture mechanism at the vinyl sites.
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影响因子：
62.1
作者：
Y. Rudich
通讯作者：
Y. Rudich
影响因子：
4.4
作者：
KING, ME;SAECKER, ME;NATHANSON, GM
通讯作者：
NATHANSON, GM
直接气液界面动力学：O(3P) 和液态烃之间的反应。
DOI：
10.1021/jp056128q
发表时间：
2006
期刊：
The journal of physical chemistry. B
影响因子：
--
作者：
Sven P K Köhler;M. Allan;M. Costen;K. McKendrick
通讯作者：
K. McKendrick
影响因子：
2.9
作者：
Nogueira, Juan J.;Vazquez, Saulo A.;Martinez-Nunez, Emilio
通讯作者：
Martinez-Nunez, Emilio
来自 Pt(111) 的 NO 的旋转排列。
DOI：
10.1039/f29898501325
发表时间：
1989
期刊：
Journal of the Chemical Society, Faraday Transactions
影响因子：
--
作者：
D. C. Jacobs;K. Kolasinski;R. Madix;R. Zare
通讯作者：
R. Zare