Ion Chemistry of Carbon Dioxide in Nonthermal Reaction with Molecular Hydrogen

Satta, Mauro; Catone, Daniele; Castrovilli, Mattea Carmen; Bolognesi, P.; Avaldi, L.; Zema, N.; Cartoni, Antonella

doi:10.1021/acs.jpca.2c01695

Cited by 4 publications

(6 citation statements)

References 38 publications

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“…The VTST approach is generally used when the reaction follows a statistic energy redistribution (local equilibrium) [23,24] but it could fail when a high-frequency vibration does not couple efficiently to others in the reaction complex and when reagents are not in thermal equilibrium with the surrounding and within the complex. In these cases, nonthermal rate coefficients must be calculated by modeling the system with the introduction of effective temperature and by correlating the temperature with the internal energy of the ion generated by synchrotron radiation, as in the case of the reaction of SO •+ with H 2 has been studied [25]. The theoretical modeling of the competitive fragmentation of excited ions has been based on the calculation of the microcanonical rate coefficient:…”

Section: Computational Methodologymentioning

confidence: 99%

Perspectives of Gas Phase Ion Chemistry: Spectroscopy and Modeling

et al. 2022

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The study of ions in the gas phase has a long history and has involved both chemists and physicists. The interplay of their competences with the use of very sophisticated commercial and/or homemade instrumentations and theoretical models has improved the knowledge of thermodynamics and kinetics of many chemical reactions, even if still many stages of these processes need to be fully understood. The new technologies and the novel free-electron laser facilities based on plasma acceleration open new opportunities to investigate the chemical reactions in some unrevealed fundamental aspects. The synchrotron light source can be put beside the FELs, and by mass spectrometric techniques and spectroscopies coupled with versatile ion sources it is possible to really change the state of the art of the ion chemistry in different areas such as atmospheric and astro chemistry, plasma chemistry, biophysics, and interstellar medium (ISM). In this manuscript we review the works performed by a joint combination of the experimental studies of ion–molecule reactions with synchrotron radiation and theoretical models adapted and developed to the experimental evidence. The review concludes with the perspectives of ion–molecule reactions by using FEL instrumentations as well as pump probe measurements and the initial attempt in the development of more realistic theoretical models for the prospective improvement of our predictive capability.

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Section: Computational Methodologymentioning

confidence: 99%

Perspectives of Gas Phase Ion Chemistry: Spectroscopy and Modeling

et al. 2022

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“…S1 for N 2 O and Section S3 of the ESI † of ref. 28 for CO 2 ), and E HT/CT is the reaction energies and E v is the vibrational energy of the species.…”

Section: Synchrotron Experimentsmentioning

confidence: 99%

Formation of H₃O⁺ and OH by CO₂ and N₂O trace gases in the atmospheric environment

Catone,

Castrovilli,

Nicolanti

et al. 2023

Phys. Chem. Chem. Phys.

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“…where the first term is the thermal energy of the reagents, the second term is the experimental collision energy (75 meV) and the third term E HT CT ⁄ tras is the relative kinetic energy produced during the reaction, and it is given by energy conservation with respect to the total reaction energy available: (6) where E INT (h) is the internal energy which remains in the X + ion at the photon energy h (see the supplementary information (SI) section 1 Figure S1 for N 2 O and section 3 of the SI of Ref 28 for CO 2 ), and E HT/CT is the reaction energies and E v is the vibrational energy of the species.…”

Section: Microcanonical Branching Ratiomentioning

confidence: 99%

“…In this scenario, the present manuscript focuses on an experimental and theoretical study of the ion chemistry of carbon dioxide and nitrous oxide radical cation with water. These molecules, as observed in the reaction of sulfur dioxide radical cation with water, [14][15][16] can catalyze a fast production of hydronium ions and hydroxyl radical OH, the main oxidant present in the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Formation of H3O+ and OH by CO2 and N2O trace gases in the atmospheric environment

Satta

Cartoni

Catone

et al. 2023

Preprint

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The impact of cosmic rays’ energetic subatomic particles on climate and global warming is still controversial and under debate. Cosmic rays produce ions that can trigger fast reactions affecting chemical networks in the troposphere and stratosphere especially when a large amount of relevant trace gases such as carbon dioxide, methane, sulfur dioxide and water are injected by volcanic eruptions. This work focuses on synchrotron experiments and an ab initio theoretical study of the ion chemistry of carbon dioxide and nitrous oxide radical cations reacting with water. These molecules catalyze a fast exothermic formation of hydronium ions H3O+ and the hydroxyl radical OH, the main oxidant in the atmosphere. Moreover, theoretical calculations demonstrate that at the end of the catalytic cycle, CO2 and N2O are produced vibrationally excited and subsequently they quench in the microsecond time scale by collision with the surrounding atmospheric molecules at the pressure and temperature of upper-troposphere/stratosphere. The chemistry involved in these reactions has a strong impact on the oxidant capacity of the atmosphere, on the sulfate aerosol production, on the cloud formation and eventually on the chemical networks controlling climate and global warming models.

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Ion Chemistry of Carbon Dioxide in Nonthermal Reaction with Molecular Hydrogen

Cited by 4 publications

References 38 publications

Perspectives of Gas Phase Ion Chemistry: Spectroscopy and Modeling

Perspectives of Gas Phase Ion Chemistry: Spectroscopy and Modeling

Formation of H₃O⁺ and OH by CO₂ and N₂O trace gases in the atmospheric environment

Formation of H3O+ and OH by CO2 and N2O trace gases in the atmospheric environment

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