Calculating Photoabsorption Cross-Sections for Atmospheric Volatile Organic Compounds
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F22%3A43922485" target="_blank" >RIV/60461373:22340/22:43922485 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/full/10.1021/acsearthspacechem.1c00355" target="_blank" >https://pubs.acs.org/doi/full/10.1021/acsearthspacechem.1c00355</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acsearthspacechem.1c00355" target="_blank" >10.1021/acsearthspacechem.1c00355</a>
Alternative languages
Result language
angličtina
Original language name
Calculating Photoabsorption Cross-Sections for Atmospheric Volatile Organic Compounds
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA20-15825S" target="_blank" >GA20-15825S: Towards Accurate Computational Spectroscopy: Merging Quantum Mechanics with Statistical Techniques</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
ACS Earth and Space Chemistry
ISSN
2472-3452
e-ISSN
2472-3452
Volume of the periodical
6
Issue of the periodical within the volume
1
Country of publishing house
US - UNITED STATES
Number of pages
11
Pages from-to
207-217
UT code for WoS article
000734044900001
EID of the result in the Scopus database
2-s2.0-85122009756