In this work, a previous quantum wave-packet time-dependent study (D. De Fazio, A. Aguado and C. Petrongolo, Non-adiabatic quantum dynamics of the dissociative charge transfer He+ + H2 → He + H + H+. Front. Chem., 2019, 7, A249) on the charge-transfer dissociation of the hydrogen molecule by the helium cation is continued, extending the calculation to eight rotational H2 reactant states. New data are required to obtain convergent (within about 1 percent) Boltzmann-averaged thermal rate constants up to 1000 Kelvin, which are necessary to provide reliable reaction yields for astrophysical and cosmological computational models. To the best of our knowledge, these are the first quantum mechanical thermal rate constant calculations for a dissociative charge transfer process. As shown in the previous work for the effect of vibrations, a relevant role of rotations is found, and the use of roto-vibrational ground state rate constant only, as often employed in astrophysical model is a poor approximation, especially above room temperature. The large computational scaling of wave-packet methods for excited rotational reactant states, due to the linear increase of the number of projections of the diatomic rotational angular momentum along the internuclear axis, is handled efficiently in the calculations, providing an accurate documentation for developing approximations that are needed to extend the calculations to higher temperatures. A particular effort has been made to better clarify the reaction mechanism, which indicated the key roles of the geometrical phase and non-adiabatic effects. Additionally, the rich resonance pattern, which is the principal reaction mechanism at these temperatures and represents the main source of the computational load, is analyzed and rationalized in detail according to the resonance analysis.

Sulfur-doped graphene (SG) has attracted considerable interest for energy conversion and storage applications. However, the relevant catalytic mechanisms remain obscure due to ongoing contentious debates regarding the location of dopant atoms. While theoretical studies often assume sulfur dopants preferentially reside at edge sites, experimental evidence consistently shows their homogeneous distribution throughout the carbon lattice. Here, we first demonstrated the thermal and dynamical instabilities of previously proposed models of S-bearing defects in the basal plane of SG, which were used to explain experimentally observed enhanced lithium adsorption and magnetism. We then presented new stable defect configurations in the graphene lattice that incorporate both sulfur dopants and inevitable oxygen-bearing functional groups, thereby explaining those experimental observations. These in-plane defect models provide an internally consistent explanation for the active sites and catalytic mechanisms of oxygen, nitrogen, and sulfur reduction reactions, and suggest that the catalytic performance of SG cannot be rationalized solely by edge-located sulfur dopants. In particular, several of the newly identified in-plane defects exhibit calculated activities comparable to, or in some cases exceeding, those of representative edge configurations. Our findings highlight a previously underappreciated role of basal-plane defects in sulfur-doped carbonaceous materials, encompassing both metal-free catalysts and graphene-based single-atom systems.

Comparison of kinetic parameters and reaction mechanisms between hardwood and softwood pyrolysis: insights from combined kinetics.

NOx decomposition through seaweed biocarbon as biosourced catalyst: Experimental and density functional theory approaches.

Co-pyrolysis of cotton stalks and polyethylene film: A study on synergetic effects, kinetic characteristics, and reaction mechanism

In-situ ferrous oxalate coating strategy activates nano zero-valent iron for enhanced U(VI) Removal: Efficacy and reaction mechanism

Na/Co3O4 catalysts with urchin-like morphology: Facile preparation, reaction mechanisms, and catalytic performance for soot combustion

Surface-bound sulfate radical-dominated degradation of sulfamethoxazole in the CuFe-LDH/NF/peroxymonosulfate system: The abundant hydroxyl groups and nickel foam synergistically enhancing stable efficiency mechanism.

Understanding of indium-gallium-zinc oxide wet etching in acidic solutions: Reaction mechanism, kinetics, and surface properties

Theoretical elucidation of C2H5OH and CH interaction: insights into reaction mechanisms and kinetics

High throughput method for the determination of α, β-unsaturated aldehydes in edible oils: A UV-vis analysis.

Active sites and reaction mechanisms over the catalysts for VOCs oxidation

Targeted regulation mechanism of pyrolysis reaction via ball milling pretreatment based on kinetic energy dose benefit analysis

Construction of Ru-anchored tubular carbon nitride for boosted photocatalytic degradation of norfloxacin: Unravelling synergistic mechanism of nitrogen defect engineering and photo-Fenton like reaction

High-performance Fe3O4@NiS2 to activate peroxymonosulfate for efficient removal of enrofloxacin in water: Reaction pathways and mechanism insight

Research on the combustion response behavior and reaction mechanism of Al/PTFE energetic material under laser ignition

Catalytic property tuned ozone gas sensing performance of cobalt oxides.

Deciphering the reaction mechanism and rapid Na+ diffusion in CdPS3 for efficient sodium-ion storage

Facile synthesis of ciprofloxacin-bismuth-curcumin nanocomposite to inhibit the growth and biofilm formation of some pathogenic microbes: Aspects of the gamma-irradiation effect.

Heterogeneous catalytic ozonation of bisphenol a with oxygen vacancy-rich montmorillonite supported iron oxide.