ACS Earth and Space Chemistry最新文献

{"title":"Nanoscale Analyses of X-ray Amorphous Material from Terrestrial Ultramafic Soils Record Signatures of Environmental Conditions Useful for Interpreting Past Martian Conditions","authors":"Anthony Feldman*,&nbsp;Elisabeth Hausrath,&nbsp;Elizabeth Rampe,&nbsp;Thomas Sharp,&nbsp;Oliver Tschauner,&nbsp;Antonio Lanzirotti and Mathew Newville,&nbsp;","doi":"10.1021/acsearthspacechem.4c0015810.1021/acsearthspacechem.4c00158","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00158https://doi.org/10.1021/acsearthspacechem.4c00158","url":null,"abstract":"<p >The secondary mineral assemblage of martian rocks and sediments is critical to the interpretation of past conditions on Mars. X-ray amorphous material that is variably Mg/Fe/Si-rich and Al-poor, and that likely contains secondary alteration products, makes up between 15 and 73 wt % of Gale crater materials measured by the CheMin instrument and is also prevalent on the martian surface in other locations. Despite its prevalence, the structure and origin of this material and its implications for past martian environments remains unknown. Here, we employ transmission electron microscopy and synchrotron microprobe analyses of Fe/Si/Mg-rich and Al-poor ultramafic soils from the mediterranean climate Klamath Mountains of California and subarctic climate Tablelands of Newfoundland, Canada to help interpret environmental conditions during the formation of chemically similar X-ray amorphous material in Gale crater, Mars. X-ray amorphous material includes globular amorphous silica and chemically heterogeneous nanospherical amorphous material and nanocrystalline phases. Amorphous silica is present only in soils that undergo extensive periods of cyclic freezing conditions. X-ray amorphous material from the subarctic Tablelands is significantly richer in Mg and Si than material from the warmer Klamath Mountains. Nanocrystallites in both examined soils are richer in Fe than the truly amorphous material. However, Fe-rich nanocrystallites contain significantly more Mg and Si in the subarctic Tablelands, whereas Klamath Mountains soils contain highly Fe-enriched nanocrystallites incorporating little Mg and Si and potentially contain nanocrystalline smectites. These characteristics provide helpful identifiers to interpret past environmental conditions during the formation of X-ray amorphous material both in situ and in returned samples from Mars.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"9 1","pages":"31–48 31–48"},"PeriodicalIF":2.9,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143087452","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Comparative 1H –29Si Cross-Polarization Solid-State Nuclear Magnetic Resonance Study of Opal-A and Opal-CT","authors":"Martin R. Johnston*,&nbsp;Neville J. Curtis and Jason R. Gascooke,&nbsp;","doi":"10.1021/acsearthspacechem.4c0023310.1021/acsearthspacechem.4c00233","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00233https://doi.org/10.1021/acsearthspacechem.4c00233","url":null,"abstract":"<p >We report an extensive ¹H to ²⁹Si cross-polarization (CP) nuclear magnetic resonance (NMR) investigation of a wide range of opal-AG, opal-AN and opal-CT samples, including both spectra and contact time dependent kinetics. After an extensive study of Hartmann–Hahn optimization, spin rates and power levels we are forced to conclude that the kinetics of the system is only amenable to comparative analysis rather than determination of absolute values. Q₃ peaks showed both signal growth (<i>T</i>_IS) and decay (<i>T</i>_1ρ^<i>I</i>) while Q₄ centers only showed the <i>T</i>_IS component for all opals studied, consistent with isolated proton sources in the latter. Q₂ centers are only a minor factor in most cases. Initial ¹H–²⁹Si 2D-HETCOR spectral evidence suggests that multiple Q₃ and Q₄ sites, with differing chemical shifts, are involved in the CP process. Active silicate centers and water sites may differ for single pulse (SP) and CP modes. Both SP and CP techniques are best used for comparative studies within each and between opal classes. Differing geometries are implied for all three types of opal.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2532–2545 2532–2545"},"PeriodicalIF":2.9,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Heating, Excitation, Dissociation, and Ionization of Molecules by High-Energy Photons in Planetary Atmospheres","authors":"Antonio García Muñoz*,&nbsp; and ,&nbsp;Ewan Bataille,&nbsp;","doi":"10.1021/acsearthspacechem.4c0027310.1021/acsearthspacechem.4c00273","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00273https://doi.org/10.1021/acsearthspacechem.4c00273","url":null,"abstract":"<p >Photoionization by high-energy photons creates nonthermal electrons with a broad range of energies that heat and chemically transform the atmospheres of planets. The specifics of the interactions are notably different when the gas is atomic or molecular. Motivated by the idea that molecules survive to high altitudes in some exoplanets, we built a model for the energy transfer from nonthermal electrons to the H₂O, H₂, and O₂ molecules. Our calculations show that the primary electrons of energy above about a hundred eV, a likely outcome from X-ray photoionization at moderately high atmospheric densities, expend most of their energy in ionization, dissociation, and electronic excitation collisions. In contrast, the primary electrons of less than about ten eV, such as those produced by extreme-ultraviolet photons at low densities, expend most of their energy in momentum transfer (heating), rotational, and vibrational excitation collisions. The partitioning between channels with weak thresholds is particularly sensitive to local fractional ionization. The transition between these two situations introduces a parallel transition in the way that the stellar energy is deposited in the atmosphere. Our calculations show that the nonthermal electrons enhance the ionization rate by a factor of a few or more with respect to photoionization alone but may not greatly contribute to the direct dissociation of molecules unless the local flux of far-ultraviolet photons is relatively weak. These findings highlight the importance of tracking the energy from the incident photons to the nonthermal electrons and onto the gas for problems concerned with the remote sensing and energy balance of exoplanet atmospheres.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2652–2663 2652–2663"},"PeriodicalIF":2.9,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical Insights into a Novel Ion–Ion Reaction of Methane in the Initial Stages of Hydrocarbon Growth in Space","authors":"Toshiaki Matsubara*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0024210.1021/acsearthspacechem.4c00242","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00242https://doi.org/10.1021/acsearthspacechem.4c00242","url":null,"abstract":"<p >In this article, we examine the reactions between methane molecules as a starting point for hydrocarbon growth in space and assess the effectiveness of the ion–ion reaction between CH₄⁺ and CH₄⁺ using quantum mechanical and molecular dynamics methods. We modeled the reaction starting from the dicationically ionized [CH₄···CH₄]²⁺ cluster. Initially, attractive interactions occur between the facing C–H bonds of the tetrahedral structures, which are electron-deficient. As the structure transitions to a trigonal pyramid, a bond begins to form between two carbon atoms with unpaired electrons, resulting in a metastable configuration due to the balance between Coulombic repulsion and attractive forces. The stabilization energy for C–C bond formation was 176.8 kcal/mol, with a bond formation efficiency of 32.6%, and the corresponding rate coefficient was 1.394 × 10^–2 fs^–1. This stabilization by C–C bond formation generates kinetic energy, and if sufficient energy is redistributed to the vibrational mode of the reaction, the reaction can proceed. Reactions involving C–C bond formation produced precursors of ethane, ethylene, and acetylene, such as C₂H₆²⁺, C₂H₅⁺, C₂H₄⁺, and C₂H₃⁺, as well as CH₃⁺, a key species in ion–molecule reactions in space. Even without C–C bond formation, a significant amount of CH₃⁺ was produced. Our findings underscore the importance of exploring novel ion–ion reactions to deepen our understanding of molecular growth in space.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2557–2573 2557–2573"},"PeriodicalIF":2.9,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850510","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical and In Situ FTIR Studies of the Atmospheric Sink of Methyl Dichloroacetate by •OH Radicals and Cl• Atoms: Kinetics, Product Distribution, and Mechanism","authors":"Vianni G. Straccia C,&nbsp;Alejandro L. Cardona,&nbsp;María B. Blanco,&nbsp;Oscar N. Ventura* and Mariano Teruel*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0026410.1021/acsearthspacechem.4c00264","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00264https://doi.org/10.1021/acsearthspacechem.4c00264","url":null,"abstract":"<p >The atmospheric degradation of methyl dichloroacetate can be initiated by ^•OH and Cl^• radicals through H atom abstraction from the alkyl groups (Cl₂HC– or –CH₃) of the chloroester. Product yields for the gas-phase reaction with ^•OH were determined experimentally in a 480 L Pyrex glass atmospheric-simulation reactor coupled to an in situ Fourier transform infrared (FTIR) spectrometer. In addition to those results, we present in this paper a complete degradation mechanism based on thermodynamic data obtained by identifying all critical points on the potential-energy surface for these reactions, employing density functional calculations with the M06-2X and MN15 hybrid exchange–correlation functionals and the aug-cc-pVTZ basis sets. A conformational search for reactants and transition states was performed. The energies of these conformers were later corrected at the CCSD(T,Full)-F12/complete basis set level by using the SVECV-f12 composite method. The corrected energies were then used to obtain the theoretical rate coefficients in a multiconformer approach. The global rate coefficient calculated for the reaction of methyl dichloroacetate with ^•Cl atoms is (7.34 × 10^–12 cm³ molecule^–1·s^–1), and the global rate coefficient calculated for the reaction with ^•OH radicals is (1.07 × 10^–12 cm³ molecule^–1·s^–1). The identified products and their respective yield percentages for the reaction of MDCA with ^•OH were Cl₂CHCOOH (44 ± 3%), COCl₂ (43 ± 3%), and CO (41 ± 6%). The analysis of the mechanism suggests that formation of P1 (Cl₂CO, phosgene) occurs mainly by abstraction from the Cl₂HC– group since the formation of P4 (Cl₂CHC(O)OH, dichloroacetic acid) and P5 (CO, carbon monoxide) is more favorable in the path for abstraction from the –OCH₃ group. The multiconformer calculated rate constant values were compared with the values obtained employing only the low-lying TSs and with our own previous experimental studies. Branching ratios for the reaction with ^•Cl were compared to the experimental product yields.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2599–2610 2599–2610"},"PeriodicalIF":2.9,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Iodine Activation from Iodate Reduction in Aqueous Films via Photocatalyzed and Dark Reactions","authors":"Mago Reza,&nbsp;Lucia Iezzi,&nbsp;Henning Finkenzeller,&nbsp;Antoine Roose,&nbsp;Markus Ammann and Rainer Volkamer*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0022410.1021/acsearthspacechem.4c00224","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00224https://doi.org/10.1021/acsearthspacechem.4c00224","url":null,"abstract":"<p >Iodine in the atmosphere destroys ozone and can nucleate particles by formation of iodic acid, HIO₃. Recent field observations suggest iodate recycles from particles sustaining significant gas-phase IO radical concentrations (0.06 pptv) in aged stratospheric air, and in elevated dust plumes. However, laboratory evidence for iodine activation from aerosols is currently missing. Here, a series of coated-wall flow tube (CWFT) experiments test for iodine release from thin aqueous films containing iodate. Photocatalyzed reactions were studied using iron(III) citrate (Fe–Cit), Arizona Test Dust (ATD), and Fe₂O₃, along with the dark reaction of iodate with H₂O₂ at 90% RH and 293 K. Fresh films were separately irradiated with visible and UV-A light, and the efficient release of molecular iodine, I₂, was observed from all irradiated films containing photocatalysts. For films with Fe–Cit, visible light reduced larger amounts of iodate than UV-A light, activating ∼40% of iodate as I₂. The formation of oxygenated volatile organic compounds (OVOC) and iodinated OVOC was also observed. Dark exposure of films to H₂O₂ led to I₂ release in smaller amounts than suggested by Bray–Liebhafsky kinetics, consistent with H₂O₂ salting-out in the films, or possibly other reasons. Photochemical activation is enhanced by dust proxies in the film, and by aging the film with H₂O₂ in the dark prior to irradiation. These findings help explain recent field observations of elevated IO radical concentrations in lofted dust layers, and warrant the inclusion of photocatalyzed iodate reduction in atmospheric models.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2495–2508 2495–2508"},"PeriodicalIF":2.9,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00224","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Iodine Activation from Iodate Reduction in Aqueous Films via Photocatalyzed and Dark Reactions.","authors":"Mago Reza, Lucia Iezzi, Henning Finkenzeller, Antoine Roose, Markus Ammann, Rainer Volkamer","doi":"10.1021/acsearthspacechem.4c00224","DOIUrl":"10.1021/acsearthspacechem.4c00224","url":null,"abstract":"<p><p>Iodine in the atmosphere destroys ozone and can nucleate particles by formation of iodic acid, HIO₃. Recent field observations suggest iodate recycles from particles sustaining significant gas-phase IO radical concentrations (0.06 pptv) in aged stratospheric air, and in elevated dust plumes. However, laboratory evidence for iodine activation from aerosols is currently missing. Here, a series of coated-wall flow tube (CWFT) experiments test for iodine release from thin aqueous films containing iodate. Photocatalyzed reactions were studied using iron(III) citrate (Fe-Cit), Arizona Test Dust (ATD), and Fe₂O₃, along with the dark reaction of iodate with H₂O₂ at 90% RH and 293 K. Fresh films were separately irradiated with visible and UV-A light, and the efficient release of molecular iodine, I₂, was observed from all irradiated films containing photocatalysts. For films with Fe-Cit, visible light reduced larger amounts of iodate than UV-A light, activating ∼40% of iodate as I₂. The formation of oxygenated volatile organic compounds (OVOC) and iodinated OVOC was also observed. Dark exposure of films to H₂O₂ led to I₂ release in smaller amounts than suggested by Bray-Liebhafsky kinetics, consistent with H₂O₂ salting-out in the films, or possibly other reasons. Photochemical activation is enhanced by dust proxies in the film, and by aging the film with H₂O₂ in the dark prior to irradiation. These findings help explain recent field observations of elevated IO radical concentrations in lofted dust layers, and warrant the inclusion of photocatalyzed iodate reduction in atmospheric models.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2495-2508"},"PeriodicalIF":2.9,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11664648/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solar Wind Irradiation of Methane and Methane–Water Ices: A Molecular Dynamics Approach","authors":"Alessandra Ricca*,&nbsp; and ,&nbsp;Justin B. Haskins,&nbsp;","doi":"10.1021/acsearthspacechem.4c0022510.1021/acsearthspacechem.4c00225","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00225https://doi.org/10.1021/acsearthspacechem.4c00225","url":null,"abstract":"<p >Molecular dynamics simulations were performed to characterize reaction products, resulting from solar wind irradiation, namely, H⁺, of methane and methane–water ices. In our approach, we used seven 0.829 keV H⁺ (total energy of 5.8 keV), with a velocity of 400 km/s, to hit the icy surface simultaneously, and we repeated this process multiple times to simulate continuous irradiation while quenching the ice to 15 K after each irradiation to prevent excessive heating and sublimation. Our simulations produced complex organic molecules previously obtained in laboratory experiments. For methane ice, molecules containing two carbons were predominant, with ethane and ethyl radicals being the most abundant, followed by ethylene, vinyl radical, and acetylene. Hydrocarbons containing three carbons (e.g., propane, propene, and propyl) were minor products, and only a few molecules containing four carbon atoms (e.g., iso-butene, 1-methylpropylidene, and 2-buten-2-yl) formed. Products that can be formed from the reaction of 1–3 impact fragmentation events, ethane, ethyl radical, and ethylene, monotonically increased over time, while products of 3 or more impact fragmentation events, vinyl, propane, and acetylene, formed over longer time scales. The number of methane complexes decreased over time. For a methane/water (1:1) ice mixture, most of the products consisted of methyl–water complexes, and their number increased with time. All the other oxygenated and nonoxygenated products formed in small amounts due to the water solvation of radicals. For a methane/water (4:1) ice mixture, the methyl–water complexes constituted 45% of the total products, with oxygenated and nonoxygenated products being formed in almost equal amounts. For methane–water ices, the proportions of alkanes, alkenes, and alkynes were very similar to those of pure methane. Dimethyl ether and ethanol formed for both 1:1 and 4:1 methane–water ices.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2509–2521 2509–2521"},"PeriodicalIF":2.9,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsearthspacechem.4c00225","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solar Wind Irradiation of Methane and Methane-Water Ices: A Molecular Dynamics Approach.","authors":"Alessandra Ricca, Justin B Haskins","doi":"10.1021/acsearthspacechem.4c00225","DOIUrl":"10.1021/acsearthspacechem.4c00225","url":null,"abstract":"<p><p>Molecular dynamics simulations were performed to characterize reaction products, resulting from solar wind irradiation, namely, H⁺, of methane and methane-water ices. In our approach, we used seven 0.829 keV H⁺ (total energy of 5.8 keV), with a velocity of 400 km/s, to hit the icy surface simultaneously, and we repeated this process multiple times to simulate continuous irradiation while quenching the ice to 15 K after each irradiation to prevent excessive heating and sublimation. Our simulations produced complex organic molecules previously obtained in laboratory experiments. For methane ice, molecules containing two carbons were predominant, with ethane and ethyl radicals being the most abundant, followed by ethylene, vinyl radical, and acetylene. Hydrocarbons containing three carbons (e.g., propane, propene, and propyl) were minor products, and only a few molecules containing four carbon atoms (e.g., iso-butene, 1-methylpropylidene, and 2-buten-2-yl) formed. Products that can be formed from the reaction of 1-3 impact fragmentation events, ethane, ethyl radical, and ethylene, monotonically increased over time, while products of 3 or more impact fragmentation events, vinyl, propane, and acetylene, formed over longer time scales. The number of methane complexes decreased over time. For a methane/water (1:1) ice mixture, most of the products consisted of methyl-water complexes, and their number increased with time. All the other oxygenated and nonoxygenated products formed in small amounts due to the water solvation of radicals. For a methane/water (4:1) ice mixture, the methyl-water complexes constituted 45% of the total products, with oxygenated and nonoxygenated products being formed in almost equal amounts. For methane-water ices, the proportions of alkanes, alkenes, and alkynes were very similar to those of pure methane. Dimethyl ether and ethanol formed for both 1:1 and 4:1 methane-water ices.</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2509-2521"},"PeriodicalIF":2.9,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11664651/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142884795","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Subsequent Reaction of CH2(1A) with N2 Molecule as a Potentially Important Source of HCN in the Atmosphere of Titan: Studies by Quantum-Chemical and Statistical Rate Theories","authors":"Vahid Saheb*,&nbsp;","doi":"10.1021/acsearthspacechem.4c0021310.1021/acsearthspacechem.4c00213","DOIUrl":"https://doi.org/10.1021/acsearthspacechem.4c00213https://doi.org/10.1021/acsearthspacechem.4c00213","url":null,"abstract":"<p >In this theoretical research, the possibility of the formation of the significant prebiotic hydrogen cyanide molecule and other important species in Titan’s atmosphere through the subsequent reactions of singlet methylene species, ¹CH₂, with the N₂ molecule is investigated. The stationary points geometries and energies of species involved in the studied reaction are calculated by high-level quantum-chemical methods such as W1RO and CCSDT(Q) methods. Next, the rate coefficients for the formation of products are computed by sophisticated statistical rate theories including RRKM and VRC-TST. It is inferred from a previous theoretical study that CH₂NN is produced predominantly from the reaction of ¹CH₂ with N₂ in the atmosphere of Titan [<contrib-group><span>Xu, S.</span>; <span>Lin, M. C.</span></contrib-group> <cite><i>J. Phys. Chem. A</i></cite> <span>2010</span>, <em>114</em>, 5195–5204]. The reactive CH₂NN molecules react with other atmospheric species like ¹CH₂ to produce new species. According to the present study, ¹CH₂ species add to CH₂NN molecules through relatively fast barrierless processes to produce some chemically activated intermediates. These intermediates rapidly decompose to yield 2 NCH₂, HCN + CH₂NH, and C₂H₄ + N₂ products. The calculated data reveal that HCN and C₂H₄ are efficiently produced from the subsequent reaction of ¹CH₂ with N₂ molecules in the atmosphere of Titan. The following rate constant expressions are suggested for the computed rate coefficients for the production of 2 NCH₂ (<i>k</i>₁), HCN + CH₂NH (<i>k</i>₂), and C₂H₄ + N₂ (<i>k</i>₃) from ¹CH₂ + CH₂NN reaction over the temperature range 200–700 K: <i>k</i>₁ = 5.48 × 10^–10 (T/300)^0.258 exp (255/T) <i>k</i>₂ = 1.15 × 10^–14 (T/300)^0.901 exp (355/T) <i>k</i>₃ = 3.10 × 10^–10 (T/300)^−0.428 exp (130/T).</p>","PeriodicalId":15,"journal":{"name":"ACS Earth and Space Chemistry","volume":"8 12","pages":"2474–2482 2474–2482"},"PeriodicalIF":2.9,"publicationDate":"2024-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850485","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}