Institut de Ciència Molecular, Universitat de València, València 46071, Spain.
Department of Atmospheric Chemistry and Climate, Institute of Physical Chemistry Rocasolano, CSIC, Madrid 28006, Spain.
J Am Chem Soc. 2021 Nov 10;143(44):18794-18802. doi: 10.1021/jacs.1c10153. Epub 2021 Nov 2.
Sulfur trioxide (SO) and the hydroxysulfonyl radical (HOSO) are two key intermediates in the production of sulfuric acid (HSO) on Earth's atmosphere, one of the major components of acid rain. Here, the photochemical properties of these species are determined by means of high-level quantum chemical methodologies, and the potential impact of their light-induced reactivity is assessed within the context of the conventional acid rain generation mechanism. Results reveal that the photodissociation of HOSO occurs primarily in the stratosphere through the ejection of hydroxyl radicals (OH) and sulfur dioxide (SO). This may decrease the production rate of HSO in atmospheric regions with low O concentration. In contrast, the photostability of SO under stratospheric conditions suggests that its removal efficiency, still poorly understood, is key to assess the HSO formation in the upper atmosphere.
三氧化硫 (SO) 和羟磺基自由基 (HOSO) 是地球大气中硫酸 (HSO) 生成的两个关键中间体,也是酸雨的主要成分之一。在这里,通过使用高精度量子化学方法确定了这些物种的光化学性质,并在传统酸雨生成机制的背景下评估了它们光诱导反应性的潜在影响。结果表明,HOSO 的光解主要通过 OH 和 SO 的喷射在平流层中发生。这可能会降低低 O 浓度大气区域中 HSO 的生成速率。相比之下,SO 在平流层条件下的光稳定性表明,其去除效率(仍知之甚少)是评估高层大气中 HSO 形成的关键因素。