Calculating Photoabsorption Cross-Sections for Atmospheric Volatile Organic Compounds

Prlj, Antonio; Marsili, Emanuele; Hutton, Lewis; Hollas, Daniel; Shchepanovska, Darya; Glowacki, David R.; Slavíček, Petr; Curchod, Basile F.E.

Abstract

Characterizing the photochemical reactivity of transient volatile organic compounds (VOCs) in our atmosphere begins with a proper understanding of their abilities to absorb sunlight. Unfortunately, the photoabsorption cross-sections for a large number of transient VOCs remain unavailable experimentally due to their short lifetime or high reactivity. While structure–activity relationships (SARs) have been successfully employed to estimate the unknown photoabsorption cross-sections of VOCs, computational photochemistry offers another promising strategy to predict not only the vertical electronic transitions of a given molecule but also the width and shape of the bands forming its absorption spectrum. In this work, we focus on the use of the nuclear ensemble approach (NEA) to determine the photoabsorption cross-section of four exemplary VOCs, namely, acrolein, methylhydroperoxide, 2-hydroperoxy-propanal, and (microsolvated) pyruvic acid. More specifically, we analyze the influence that different strategies for sampling the ground-state nuclear density─Wigner sampling and ab initio molecular dynamics with a quantum thermostat─can have on the simulated absorption spectra. We highlight the potential shortcomings of using uncoupled harmonic modes within Wigner sampling of nuclear density to describe flexible or microsolvated VOCs and some limitations of SARs for multichromophoric VOCs. Our results suggest that the NEA could constitute a powerful tool for the atmospheric community to predict the photoabsorption cross-section for transient VOCs.

Citation

Prlj, A., Marsili, E., Hutton, L., Hollas, D., Shchepanovska, D., Glowacki, D. R., …Curchod, B. F. (2022). Calculating Photoabsorption Cross-Sections for Atmospheric Volatile Organic Compounds. ACS Earth and Space Chemistry, 6(1), 207-217. https://doi.org/10.1021/acsearthspacechem.1c00355

• Journal Article Type: Article
• Acceptance Date: Dec 3, 2021
• Online Publication Date: Dec 17, 2021
• Publication Date: 2022
• Deposit Date: Feb 16, 2022
• Publicly Available Date: Feb 16, 2022
• Journal: ACS Earth and Space Chemistry
• Electronic ISSN: 2472-3452
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 6
• Issue: 1
• Pages: 207-217
• DOI: https://doi.org/10.1021/acsearthspacechem.1c00355
• Public URL: https://durham-repository.worktribe.com/output/1215182