Kroll Jay A, Frandsen Benjamin N, Kjaergaard Henrik G, Vaida Veronica
Department of Chemistry and Biochemistry , University of Colorado Boulder , UCB 215 , Boulder , Colorado 80309 , United States.
Cooperative Institute for Research in Environmental Sciences , University of Colorado Boulder , UCB 216 , Boulder , Colorado 80309 , United States.
J Phys Chem A. 2018 May 10;122(18):4465-4469. doi: 10.1021/acs.jpca.8b03524. Epub 2018 Apr 26.
The reaction of electronically excited triplet state sulfur dioxide (SO) with water was investigated both theoretically and experimentally. The quantum chemical calculations find that the reaction leads to the formation of hydroxyl radical (OH) and hydroxysulfinyl radical (HOSO) via a low energy barrier pathway. Experimentally the formation of OH was monitored via its reaction with methane, which itself is relatively unreactive with SO, making it a suitable probe of OH production from the reaction of SO and water. This reaction has implications for the formation of OH in environments that are assumed to be depleted in OH, such as volcanic plumes. This reaction also provides a mechanism for the formation of OH in planetary atmospheres with little or no oxygen (O) or ozone (O) present.
对电子激发态三线态二氧化硫（SO）与水的反应进行了理论和实验研究。量子化学计算发现，该反应通过低能垒途径生成羟基自由基（OH）和亚磺酰羟基自由基（HOSO）。实验上，通过OH与甲烷的反应监测OH的生成，甲烷本身与SO反应性相对较低，使其成为SO与水反应生成OH的合适探针。该反应对于在假定OH含量较低的环境（如火山羽流）中OH的形成具有重要意义。该反应还为在几乎没有或不存在氧气（O）或臭氧（O）的行星大气中OH的形成提供了一种机制。
