Investigating Phase-Dependent Reactivity in Environmental Chemistry

华盛顿大学教授菲利普·里德由实验物理化学项目资助，对溶剂对与环境有关的化学反应的影响进行实验研究。卤化物光化学反应在大气中很重要；虽然实验室已经很好地研究了气相的光反应性，但对这些化合物在凝聚相(如雨滴)中的光反应性知之甚少。PI建议继续使用共振拉曼光谱(强度和时间分辨)以及飞秒泵浦-探测测量来详细研究OClO在气体和凝聚相中的光化学。然后，PI建议以类似的方式研究ClOCl、亚硝酰卤化物和烷基硝酸盐，以确定这些体系的总体趋势。这一提议的一个成功结果将是一个预测溶剂对小分子光反应性影响的模型。拟议的工作特别及时，因为大气化学家认识到，多相反应可以对整个过程做出重大贡献，因此必须包括在大气模型中。

Professor Philip Reid of University of Washington is funded by the Experimental Physical Chemistry program to perform experimental studies on the effects of solvent on chemical reactions relevant to the environment. Halooxide photochemistry is important in the atmosphere; while the gas phase photoreactivity has been well studied in the laboratory, not much is known about photoreactivity of these compounds in the condensed phase (e.g. rain droplets). The PI proposes to continue detailed studies on OClO photochemistry in both gas and condensed phases using resonance Raman spectroscopy (intensity and time-resolved) as well as femtosecond pump-probe measurements. The PI then proposes to study ClOCl, nitrosyl halides and alkyl nitrates in a similar manner to establish general trends in these systems. A successful outcome of this proposal would be a model for the prediction of solvent effects on the photoreactivity of small molecules. The proposed work is especially timely because of recognition by atmospheric chemists that heterogeneous reactions can contribute significantly to overall processes, and therefore must be included in models of the atmosphere.