A1 Journal article (refereed)
Theoretical characterization of the photochemical reaction CO2+O(3P)→CO+O2 related to experiments in solid krypton (2020)

Grigorenko, B. L., Duarte, L., Polyakov, I. V., & Nemukhin, A. V. (2020). Theoretical characterization of the photochemical reaction CO2+O(3P)→CO+O2 related to experiments in solid krypton. Chemical Physics Letters, 746, Article 137303. https://doi.org/10.1016/j.cplett.2020.137303

JYU authors or editors

Ferreira de Deus da Rocha Duarte, Luis

Publication details

All authors or editors: Grigorenko, Bella L.; Duarte, Luís; Polyakov, Igor V.; Nemukhin, Alexander V.

Journal or series: Chemical Physics Letters

ISSN: 0009-2614

eISSN: 1873-4448

Publication year: 2020

Volume: 746

Article number: 137303

Publisher: Elsevier

Publication country: Netherlands

Publication language: English

DOI: https://doi.org/10.1016/j.cplett.2020.137303

Publication open access: Not open

Publication channel open access:

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/68093

Abstract

Formation and decomposition of the complex of carbon dioxide and atomic oxygen are characterized by quantum chemistry methods aiming to rationalize experimental studies in solid krypton. The observed FTIR spectra reflected the temporal evolution of the system after irradiation showing the bands of reactants, intermediates and products. Advanced quantum chemistry calculations show that the T-shape complex CO2…O(3P) can be formed in the matrix. Its excitation by the 193 nm light results in the charge-transfer state CO2+…O-, which evolves to the reaction intermediate CO3. The latter species decomposes to CO + O2 following pathways on the excited state energy surfaces.

Keywords: carbon dioxide; oxygen; molecules; photochemistry; quantum chemistry

Free keywords: carbon dioxide; atomic oxygen; intermolecular complexes; matrix isolation; photochemistry; excited states; quantum chemistry

Fields of science: