On the Electronic Origins of the Different Behaviors of S+ and S2+/2+ in Methane Activation

Yu, Mincheng; Ruan, Jiancheng; Qian, Chao; Chen, Xinzhi; Ge, Xin; Zhou, Shaodong

doi:10.1002/slct.202002907

Cited by 5 publications

(3 citation statements)

References 59 publications

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“…These authors assumed that H 3 CS + is formed, which is impossible because S + is a quadruplet while H 3 CS + is a triplet, and it would be impossible energetically for the spin conservation rules. Indeed, Yu et al (2020) found that the corrected product seen by Smith et al (1981) is H 2 CSH + (singlet) and not H 3 CS + , as corroborated by our calculations that found the channel producing H 2 CSH + to be exothermic. Please note that to reintroduce the reaction with the correct reaction channel (H 2 CSH + ) would require revising all the reactions involving H 3 CS + and H 2 CSH + , which is beyond the scope of the present work.…”

Section: Comparison With the Umist Databasesupporting

confidence: 84%

The GRETOBAPE Gas-phase Reaction Network: The Importance of Being Exothermic

Tinacci

Ferrada-Chamorro

Ceccarelli

et al. 2023

ApJS

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The gas-phase reaction networks are the backbone of astrochemical models. However, due to their complexity and nonlinear impact on the astrochemical modeling, they can be the first source of error in the simulations if incorrect reactions are present. Over time, following the increasing number of species detected, astrochemists have added new reactions, based on laboratory experiments and quantum mechanics (QM) computations, as well as reactions inferred by chemical intuition and the similarity principle. However, sometimes no verification of their feasibility in the interstellar conditions, namely their exothermicity, was performed. In this work, we present a new gas-phase reaction network, GRETOBAPE, based on the KIDA2014 network and updated with several reactions, cleaned from endothermic reactions not explicitly recognized as such. To this end, we characterized all the species in the GRETOBAPE network with accurate QM calculations. We found that ∼5% of the reactions in the original network are endothermic, although most of them are reported as barrierless. The reaction network of Si-bearing species is the most impacted by the endothermicity cleaning process. We also produced a cleaned reduced network, GRETOBAPE-red, to be used to simulate astrochemical situations where only C-, O-, N-, and S-bearing species with less than six atoms are needed. Finally, the new GRETOBAPE network, its reduced version, and the database with all the molecular properties are made publicly available. The species property database can be used in the future to test the feasibility of possibly new reactions.

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Section: Comparison With the Umist Databasesupporting

confidence: 84%

The GRETOBAPE Gas-phase Reaction Network: The Importance of Being Exothermic

Tinacci

Ferrada-Chamorro

Ceccarelli

et al. 2023

ApJS

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“…The experiments were performed in a self-designed, quadrupole-ion trap mass spectrometer (see Figure 1), as described elsewhere. 41,42 The Osmium-carbide cluster ions OsC 2 + or Iridium-carbide cluster ions IrC controlled by pulsed valves. The ions are sent into the quadrupole mass filter through a 5 mm diameter hole of a skimmer, and then the ions are guided into the ion trap (also the reaction cell) through a 5 mm diameter hole of the electric shielding plate and react with CH 4 or 13 CH 4 (reaction time is 10 ms), which is introduced into the reaction cell via a leak valve.…”

Section: Methodsmentioning

confidence: 99%

“…The experiments were performed in a self-designed, quadrupole-ion trap mass spectrometer (see Figure ), as described elsewhere. , The Osmium-carbide cluster ions OsC 2 + or Iridium-carbide cluster ions IrC 2 + are generated by pulsed laser (532 nm, Nd:YAG) ablation of a rotating and translating solid target (compressed Osmium and graphite powder (1:2; volume ratio) or Iridium and graphite powder (1:2.5; volume ratio)) in the presence of Ar carrier gas (99.999%) with a stationary backing pressure of 0.5 MPa. The carrier gas is controlled by pulsed valves.…”

Section: Experimental and Computational Methodsmentioning

confidence: 99%

Carbon-Atom Exchange between [MC₂]⁺ (M = Os and Ir) and Methane: on the Thermodynamic and Dynamic Aspects

Li,

Qian,

et al. 2024

J. Phys. Chem. A

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Gas-phase reactions of [OsC 2 ] + and [IrC 2 ] + with methane at ambient temperature have been studied using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. Both [OsC 2 ] + and [IrC 2 ] + undergo carbon-atom exchange reactions with methane. The associated mechanisms for the two systems are found to be similar. The differences in the rates of carbon isotope exchange reactions of methane with [MC 2 ] + (M = Os and Ir) are explained by several factors like the energy barrier for the initial H 3 C−H bond breaking processes, the molecular dynamics, orbital interactions, and the Hbinding energies of the pivotal steps. Besides, the number of participating valence orbitals might be one of the keys to regulate the rate in the key step. The present findings may provide useful ideas and inspiration for designing similar processes.

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Toward the Rational Design of an OsM₄ Center for Methane Activation: Gas-Phase Result-Derived Neural Network Model

Li,

Wang,

Qian

et al. 2024

J. Phys. Chem. A

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Gas-phase reactions of [OsB x ] + (x = 1−4) with methane at ambient temperature have been studied by using quadrupole-ion trap mass spectrometry combined with quantum chemical calculations. The [OsB x ] + (x = 1−4) cluster ions can undergo dehydrogenation reactions with methane. Comprehensive analysis of the [OsB x ] + /CH 4 (x = 1−4) system with Oscomplexes ([OsC y ] + (y = 1−3) and [OsO z ] + (z = 1−3)) shows that the large polarity of the cluster and the high sum of the pair energies between Os and the ligand in the ETS-NOCV combine to promote the ability of the cluster to activate methane. Cluster polarity may induce heterolytic cleavage of the C−H bond, and the sum of the pair energies of the fragments may reduce the cluster orbital energy to match the methane orbital and improve the cluster stability. The synergistic interplay of these two factors may offer a viable approach for the activation of methane in the condensed phase, which involves modulating the coordination environment of the active sites to enhance the stability and facilitate C−H bond cleavage and the degree of matching with methane orbitals. A nonlinear function is used to extract second-order characteristic features that have a significant impact on the energy difference based on the limited energy difference data of the OsB m C n O l H k units. A neural network model is next designed to predict the reaction barrier for methane conversion by OsM 4 + (M = C, N, O, Al, Si, or P) with high accuracy.

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On the Electronic Origins of the Different Behaviors of S⁺ and S₂^+/2+ in Methane Activation

Cited by 5 publications

References 59 publications

The GRETOBAPE Gas-phase Reaction Network: The Importance of Being Exothermic

The GRETOBAPE Gas-phase Reaction Network: The Importance of Being Exothermic

Carbon-Atom Exchange between [MC₂]⁺ (M = Os and Ir) and Methane: on the Thermodynamic and Dynamic Aspects

Toward the Rational Design of an OsM₄ Center for Methane Activation: Gas-Phase Result-Derived Neural Network Model

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On the Electronic Origins of the Different Behaviors of S+ and S2+/2+ in Methane Activation

Cited by 5 publications

References 59 publications

The GRETOBAPE Gas-phase Reaction Network: The Importance of Being Exothermic

The GRETOBAPE Gas-phase Reaction Network: The Importance of Being Exothermic

Carbon-Atom Exchange between [MC2]+ (M = Os and Ir) and Methane: on the Thermodynamic and Dynamic Aspects

Toward the Rational Design of an OsM4 Center for Methane Activation: Gas-Phase Result-Derived Neural Network Model

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On the Electronic Origins of the Different Behaviors of S⁺ and S₂^+/2+ in Methane Activation

Carbon-Atom Exchange between [MC₂]⁺ (M = Os and Ir) and Methane: on the Thermodynamic and Dynamic Aspects

Toward the Rational Design of an OsM₄ Center for Methane Activation: Gas-Phase Result-Derived Neural Network Model