UV absorption of Criegee intermediates: quantitative cross sections from high-level ab initio theory
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F18%3A43916691" target="_blank" >RIV/60461373:22340/18:43916691 - isvavai.cz</a>
Result on the web
<a href="https://pubs.rsc.org/en/content/articlelanding/2018/cp/c8cp00199e/unauth#!divAbstract" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2018/cp/c8cp00199e/unauth#!divAbstract</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/c8cp00199e" target="_blank" >10.1039/c8cp00199e</a>
Alternative languages
Result language
angličtina
Original language name
UV absorption of Criegee intermediates: quantitative cross sections from high-level ab initio theory
Original language description
Criegee intermediates (CIs) are increasingly recognized as important intermediates in atmospheric and combustion chemistry. Modelling in these fields requires reliable characterization of the CI's UV absorption cross sections. Different experimental approaches provided seemingly contradictory results both for the simplest CI as well as for higher analogues. To resolve these discrepancies, we model simultaneously the positions, widths, shapes and absolute intensities of the first absorption bands of CIs using the semiclassical reflection principle approach based on the path integral molecular dynamics. The UV spectra were efficiently processed via the kernel density estimation method. We show that the multireference character complicates the description of the system and the appropriate treatment of the electron correlation is vital. Multi-reference methods with dynamical correlation are problematic due to high sensitivity of the results with respect to the active space. Single-reference based methods become reliable once the triple excitations components are included. Interestingly, the very similar CC2 and ADC(2) methods provide highly conflicting results which are, however, reconciled at the CC3 and ADC(3) levels. To calculate the spectra of higher CIs, we introduce composite EOM-CCSD/T and CC2/3 methods providing excellent absorption cross sections at an acceptable computational cost. We provide the first absolute intensities for individual conformers of the CH3CHOO molecule.
Czech name
—
Czech description
—
Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA17-04068S" target="_blank" >GA17-04068S: Molecular Clusters as Unique Nano-reactors: Controlling Chemistry with Photons and Electrons</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2018
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Physical Chemistry Chemical Physics
ISSN
1463-9076
e-ISSN
—
Volume of the periodical
20
Issue of the periodical within the volume
9
Country of publishing house
GB - UNITED KINGDOM
Number of pages
10
Pages from-to
6421-6430
UT code for WoS article
000429280100043
EID of the result in the Scopus database
2-s2.0-85042799519