| Autor: |
Anglada JM; Departament de Química Biològica (IQAC - CSIC), c/Jordi Girona 18, Barcelona E-08034, Spain., Martins-Costa MTC; Laboratoire de Physique et Chimie Théoriques, UMR CNRS 7019, University of Lorraine, CNRS, BP 70239, Vandoeuvre-lès-Nancy 54506, France., Francisco JS; Department of Earth and Environmental Science and Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6316, United States., Ruiz-López MF; Laboratoire de Physique et Chimie Théoriques, UMR CNRS 7019, University of Lorraine, CNRS, BP 70239, Vandoeuvre-lès-Nancy 54506, France. |
| Abstrakt: |
The triplet excited states of sulfur dioxide can be accessed in the UV region and have a lifetime large enough that they can react with atmospheric trace gases. In this work, we report high level ab initio calculations for the reaction of the a 3 B 1 and b 3 A 2 excited states of SO 2 with weak and strong acidic species such as HCOOH and HNO 3 , aimed to extend the chemistry reported in previous studies with nonacidic H atoms (water and alkanes). The reactions investigated in this work are very versatile and follow different kinds of mechanisms, namely, proton-coupled electron transfer ( pcet ) and conventional hydrogen atom transfer ( hat ) mechanisms. The study provides new insights into a general and very important class of excited-state-promoted reactions, opening up interesting chemical perspectives for technological applications of photoinduced H-transfer reactions. It also reveals that atmospheric triplet chemistry is more significant than previously thought. |
