Ab Initio Study of Electronic States of Astrophysically Important Molecules

Valiev, Rashid R.; Berezhnoy, A. A.; Minaev, B. F.; Chernov, V. E.; Cherepanov, Victor N.

doi:10.1007/s11182-016-0803-y

Cited by 9 publications

(3 citation statements)

References 37 publications

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“…Recently, a simple and fast model was developed for calculating photolysis cross-sections [34]. This model was applied to many diatomic molecules, including oxides, fluorides and chlorides of alkali metals [34][35][36]. The photolysis rate constants for these species were calculated in the exospheres of the Moon, Mercury and satellites of Jupiter using the experimentally measured solar flux.…”

Section: Peroxyl Radicals (Ro _mentioning

confidence: 99%

Is either direct photolysis or photocatalysed H-shift of peroxyl radicals a competitive pathway in the troposphere?

Valiev

Kurtén

2020

R. Soc. open sci.

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Peroxyl radicals (RO O . ) are key intermediates in atmospheric chemistry, with relatively long lifetimes compared to most other radical species. In this study, we use multireference quantum chemical methods to investigate whether photolysis can compete with well-established RO O . sink reactions. We assume that the photolysis channel is always RO O . + h ν => RO + O( 3 P). Our results show that the maximal value of the cross-section for this channel is σ = 1.3 × 10 −18 cm 2 at 240 nm for five atmospherically representative peroxyl radicals: CH 3 O O . , C(O)HCH 2 O O . , CH 3 CH 2 O O . , HC(O)O O . and CH 3 C(O)O O . . These values agree with experiments to within a factor of 2. The rate constant of photolysis in the troposphere is around 10 −5 s −1 for all five RO O . . As the lifetime of peroxyl radicals in the troposphere is typically less than 100 s, photolysis is thus not a competitive process. Furthermore, we investigate whether or not electronic excitation to the first excited state (D 1 ) by infrared radiation can facilitate various H-shift reactions, leading, for example, in the case of CH 3 O O . to formation of O . H and CH 2 O or HO O . and CH 2 products. While the activation barriers for H-shifts in the D 1 state may be lower than in the ground state (D 0 ), we find that H-shifts are unlikely to be competitive with decay back to the D 0 state through internal conversion, as this has a rate of the order of 10 13 s −1 for all studied systems.

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Section: Peroxyl Radicals (Ro _mentioning

confidence: 99%

Is either direct photolysis or photocatalysed H-shift of peroxyl radicals a competitive pathway in the troposphere?

Valiev

Kurtén

2020

R. Soc. open sci.

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“…Além disso, o estado 2 2 Π está amplamente correlacionado com A 2 Σ + e X 2 Π em ∼ 6,0 a 0 . Qualitativamente, Valiev e colaboradores [260] afirmaram que, na transição A-X, o elemento da matriz ASO é determinado principalmente pelo átomo de oxigênio, com 0,5ζ O , em que ζ O é a constante ASO para o átomo de oxigênio igual a 153 cm −1 [261]. Para confirmar esta hipótese calculamos o ζ Li para o átomo de lítio.…”

Section: Aso (Cmunclassified

“…A este respeito, calculamos o acoplamento spin-órbita de 0,33 cm −1 , em boa concordância com o valor de 0,34 cm −1 reportado por Lackner et al [262]. Portanto, o valor ζ Li é insignificante, apoiando descobertas anteriores [260].…”

Section: Aso (Cmunclassified

Estrutura eletrônica, espectroscopia e dinâmica quase-clássica de sistemas moleculares: um estudo teórico

Silva¹

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Neste trabalho, cálculos de estrutura eletrônica foram realizados visando investigar espécies formadas de [Li,N,O,S]. Através deste estudo, foi possível identificar que o acoplamento spin-órbita possui papel fundamental nos espectros moleculares dos diátomos N2, NO e LiO. Em particular, usamos os resultados obtidos para o radical NO a fim de examinar a técnica de aprisionamento por spin. Esta técnica tem por finalidade detectar radicais livres com de curtos tempos de vida em sistemas biológicos. Uma proposta de construção de superfície de energia potencial para a espécie LiS2 é discutida utilizando como base os resultados para a diatômica LiS. Para o N2, nossas predições indicam um novo sistema de bandas nunca antes observado. Além do mais, considerando a metodologia das trajetórias quase-clássicas, analisou-se a formação do mínimo de Van der Waals ArSO2 gerado a partir de colisões entre o átomo de argônio e o dióxido de enxofre.

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Study of the High-Resolution Fourier Spectrum of the ν9 and ν2 + ν7 + ν8 Bands of the С2D4 Molecule

et al. 2019

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Ab Initio Study of Electronic States of Astrophysically Important Molecules

Cited by 9 publications

References 37 publications

Is either direct photolysis or photocatalysed H-shift of peroxyl radicals a competitive pathway in the troposphere?

Is either direct photolysis or photocatalysed H-shift of peroxyl radicals a competitive pathway in the troposphere?

Estrutura eletrônica, espectroscopia e dinâmica quase-clássica de sistemas moleculares: um estudo teórico

Study of the High-Resolution Fourier Spectrum of the ν9 and ν2 + ν7 + ν8 Bands of the С2D4 Molecule

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