New insights into martian atmospheric chemistry

Boxe, C. S.; Francisco, Joseph S.; Shia, Run‐Lie; Yung, Yuk L.; Nair, H.; Liang, Mao‐Chang; Saiz‐Lopez, Alfonso

doi:10.1016/j.icarus.2014.07.023

Cited by 11 publications

(11 citation statements)

References 37 publications

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“…[37][38][39][40]42 HOCO is an important intermediate in combustion and atmospheric chemistry and it is also assumed to be involved in the formation of prebiotic molecules in the interstellar medium. [46][47][48][49][50] This radical has two conformers, the trans form being lower in energy than the cis form by about 500 cm À1 . It has been shown that trans-HOCO can be produced in low-temperature matrices upon photolysis or radiolysis of some CO-or CO 2 -containing intermolecular complexes.…”

Section: Introductionmentioning

confidence: 99%

VUV photochemistry of the H₂O⋯CO complex in noble-gas matrices: formation of the OH⋯CO complex and the HOCO radical

Ryazantsev

Duarte

Feldman

et al. 2017

Phys. Chem. Chem. Phys.

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Vacuum ultraviolet (VUV, 130-170 nm) photochemistry of the HOCO complex is studied by matrix-isolation infrared spectroscopy. The HOCO complexes in Ne, Ar, Kr, and Xe matrices are generated by ultraviolet (UV, 193 and 250 nm) photolysis of formic acid (HCOOH). VUV photolysis of the HOCO complexes is found to lead to the formation of the OHCO radical-molecule complexes and trans-HOCO radicals. It is shown that the matrix material, local matrix morphology, and possibly the HOCO complex geometry strongly affect the VUV photolysis pathways. The intrinsic reactivity of the matrix-isolated OHCO complex resulting in the formation of trans-HOCO is directly demonstrated for the first time. This reaction occurs in Ar, Kr, and Xe matrices upon annealing above 25 K and may proceed over the barrier. The case of a Ne matrix is very special because the formation of trans-HOCO from the OHCO complex is observed even at the lowest experimental temperature (4.5 K), which is in sharp contrast to the other matrices. It follows that quantum tunneling is probably involved in this process in the Ne matrix at such a low temperature. Infrared light also promotes this reaction in the Ne matrix at 4.5 K, which is not the case in the other matrices. The last findings show the effect of the environment on the tunneling and infrared-induced rates of this fundamental chemical reaction.

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Section: Introductionmentioning

confidence: 99%

VUV photochemistry of the H₂O⋯CO complex in noble-gas matrices: formation of the OH⋯CO complex and the HOCO radical

Ryazantsev

Duarte

Feldman

et al. 2017

Phys. Chem. Chem. Phys.

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“…Therefore, we apply for the first time the computer algorithm PAP to the output of the updated version of the JPL/Caltech KINETICS model of the Martian atmosphere (Nair et al, 1994;Boxe et al, 2014) to identify all significant chemical pathways and quantify their contribution to O 3 formation and consumption up to 80 km altitude.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

“…For the chemical pathway analysis, we used the steady state solution of the photochemical model for fixed temperature and pressure profiles (for details see Nair et al, 1994). The chemical reaction system includes 149 reactions (for details see Stock et al, 2012a;Boxe et al, 2014). In contrast to Stock et al (2012a), we distinguish between the excited state O 2 ( 1 ∆) and the ground state O 2 ( 3 Σ) of molecular oxygen.…”

Section: Martian Atmospheric Photochemical Column Modelmentioning

confidence: 99%

“…In contrast to Stock et al (2012a), we distinguish between the excited state O 2 ( 1 ∆) and the ground state O 2 ( 3 Σ) of molecular oxygen. Additionally, the HCO 2 chemistry introduced by Boxe et al (2014) is included in the chemical model. Reaction rate coefficients are updated according to Sander et al (2011).…”

Section: Martian Atmospheric Photochemical Column Modelmentioning

confidence: 99%

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A detailed pathway analysis of the chemical reaction system generating the Martian vertical ozone profile

Stock

Blaszczak-Boxe

Lehmann

et al. 2017

Icarus

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A detailed pathway analysis of the chemical reaction system generating the Martian vertical ozone profile, Icarus (2016), doi: 10.1016/j.icarus. 2016.12.012 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. ACCEPTED MANUSCRIPTA C C E P T E D M A N U S C R I P T Highlights• Determination of all significant O 3 producing and consuming pathways and quantification of their contributions in the Martian atmosphere with help of an automated computer algorithm.• O 3 production results from CO 2 and O 2 photolysis.• O 3 is consumed by catalytic cycles involving HO x (=H+OH+HO 2 ).• The Martian atmosphere can be divided into two chemically distinct re-gions according to the O( 3 P):O 3 ratio.• Vertical transport of O( 3 P) from upper layers downwards into the O 3 layer at around 50 km altitude provides an additional source of O x (=O+O 3 ), which is pivotal to the formation of the Martian O3 volume mixing ratio maximum. AbstractAtmospheric chemical composition is crucial in determining a planet's atmospheric structure, stability, and evolution. Attaining a quantitative understanding of the essential chemical mechanisms governing atmospheric composition is nontrivial due to complex interactions between chemical species. Trace species, for example, can participate in catalytic cycles -affecting the abundance of major and other trace gas species. Specifically, for Mars, such cycles dictate the abundance of its primary atmospheric constituent, carbon dioxide (CO 2 ), but also for one of its trace gases, ozone (O 3 ). The identification of chemical pathways/cycles by hand is extremely demanding; hence, the application of numerical methods, such as the Pathway Analysis Program (PAP), is crucial to analyze and quantitatively exemplify chemical reaction networks. Here, we carry out the first automated quantitative chemical pathway analysis of Mars' atmosphere with respect to O 3 . PAP was applied to JPL/Caltech's 1-D updated photochemical Mars model's output data. We determine all significant chemical pathways and their contribution to O 3 production and consumption (up to 80 km) in order to investigate the mechanisms causing the characteristic shape of the O 3 volume mixing ratio profile, i.e. a ground layer maximum and an ozone layer at ∼ 50 km. These pathways explain why an O 3 layer is present, why it is located at that particular altitude and what the different processes forming the near-surface and middle atmosphere O 3 maxima are. Furthermore, we show that the Martian atmosphere can be divided into two chemically distinct regions according to the O(

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“…3 While these atoms are mostly removed by quenching to the ground state through collisions with CO2, 4 a small fraction of these atoms react with H2 and H2O, present at trace levels generating OH radicals. 5 The subsequent reaction of OH radicals with CO acts to regenerate CO2, helping to maintain the stability of the Martian atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Experimental and theoretical studies of the gas-phase reactions of O(¹D) with H₂O and D₂O at low temperature

Hickson

Bhowmick

Suleimanov

et al. 2021

Phys. Chem. Chem. Phys.

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New insights into martian atmospheric chemistry

Abstract: 3

Cited by 11 publications

References 37 publications

VUV photochemistry of the H₂O⋯CO complex in noble-gas matrices: formation of the OH⋯CO complex and the HOCO radical

VUV photochemistry of the H₂O⋯CO complex in noble-gas matrices: formation of the OH⋯CO complex and the HOCO radical

A detailed pathway analysis of the chemical reaction system generating the Martian vertical ozone profile

Experimental and theoretical studies of the gas-phase reactions of O(¹D) with H₂O and D₂O at low temperature

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New insights into martian atmospheric chemistry

Abstract: 3

Cited by 11 publications

References 37 publications

VUV photochemistry of the H2O⋯CO complex in noble-gas matrices: formation of the OH⋯CO complex and the HOCO radical

VUV photochemistry of the H2O⋯CO complex in noble-gas matrices: formation of the OH⋯CO complex and the HOCO radical

A detailed pathway analysis of the chemical reaction system generating the Martian vertical ozone profile

Experimental and theoretical studies of the gas-phase reactions of O(1D) with H2O and D2O at low temperature

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VUV photochemistry of the H₂O⋯CO complex in noble-gas matrices: formation of the OH⋯CO complex and the HOCO radical

VUV photochemistry of the H₂O⋯CO complex in noble-gas matrices: formation of the OH⋯CO complex and the HOCO radical

Experimental and theoretical studies of the gas-phase reactions of O(¹D) with H₂O and D₂O at low temperature