| Title: | A Theoretical Perspective on the Actinic Photochemistry of 2-Hydroperoxypropanal |
| Author(s): | Marsili E; Prlj A; Curchod BFE; |
| Address: | "Centre for Computational Chemistry, School of Chemistry, University of Bristol, Bristol BS8 1TS, U.K" |
| ISSN/ISBN: | 1520-5215 (Electronic) 1089-5639 (Print) 1089-5639 (Linking) |
| Abstract: | "The photochemical reactions triggered by the sunlight absorption of transient volatile organic compounds in the troposphere are notoriously difficult to characterize experimentally due to the unstable and short-lived nature of these organic molecules. Some members of this family of compounds are likely to exhibit a rich photochemistry given the diversity of functional groups they can bear. Even more interesting is the photochemical fate of volatile organic compounds bearing more than one functional group that can absorb light horizontal line this is the case, for example, of alpha-hydroperoxycarbonyls, which are formed during the oxidation of isoprene. Experimental observables characterizing the photochemistry of these molecules like photoabsorption cross-sections or photolysis quantum yields are currently missing, and we propose here to leverage a recently developed computational protocol to predict in silico the photochemical fate of 2-hydroperoxypropanal (2-HPP) in the actinic region. We combine different levels of electronic structure methods horizontal line SCS-ADC(2) and XMS-CASPT2 horizontal line with the nuclear ensemble approach and trajectory surface hopping to understand the mechanistic details of the possible nonradiative processes of 2-HPP. In particular, we predict the photoabsorption cross-section and the wavelength-dependent quantum yields for the observed photolytic pathways and combine them to determine in silico photolysis rate constants. The limitations of our protocol and possible future improvements are discussed" |
| Notes: | "PubMed-not-MEDLINEMarsili, Emanuele Prlj, Antonio Curchod, Basile F E eng 2022/07/29 J Phys Chem A. 2022 Aug 18; 126(32):5420-5433. doi: 10.1021/acs.jpca.2c03783. Epub 2022 Jul 28" |
