The relativistic correction to the dissociation energy of H_{2}, D_{2}, and HD molecules has been accurately calculated without expansion in the small electron-nucleus mass ratio. The obtained results indicate the significance of nonadiabatic effects and resolve the discrepancy of theoretical predictions with recent experimental values for H_{2} and D_{2}. While the theoretical accuracy is now significantly improved and is higher than the experimental one, we observe about 3σ discrepancy for the dissociation energy of HD, which requires further investigation.
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http://dx.doi.org/10.1103/PhysRevLett.121.073001 | DOI Listing |
J Phys Chem A
January 2025
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, China.
High-level multireference configuration interaction plus Davidson correction (MRCI + Q) calculation method was employed to determine the potential energy curves (PECs) of 10 Λ-S states, which come from the first and second dissociation channels of the SbP molecule, as well as 34 Ω states considering the spin-orbit coupling (SOC) effect. By solving the Schrödinger equation for nuclear motion, spectroscopic constants for the ground state XΣ and low-lying excited states were obtained and compared with experimental data. The excellent agreement indicates the reliability of our calculations.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Tianjin University, Department of Chemistry, #92, Weijin Road, Nankai District, Department of Chemistry, School of Science, Tianjin University, 300072, Tianjin, CHINA.
Electrochemical reductive deuteration of nitriles is a promising strategy for synthesizing deuterated amines with D2O as the deuterated source. However, this reaction suffers from high overpotentials owing to the sluggish D2O dissociation kinetics and high thermodynamic stability of the C≡N triple bond. Here, low-coordinated copper (LC-Cu) is designed to decrease the overpotential for the electrosynthesis of the precursor of Melatonin-d4, 5-methoxytryptamine-d4, by 100 mV with a 68% yield (Faraday efficiency), which is 4 times greater than that of high-coordinated copper (HC-Cu).
View Article and Find Full Text PDFAdv Sci (Weinh)
January 2025
Division of Chemical and Material Metrology, Korea Research Institute of Standards and Science (KRISS), Daejeon, 34133, Republic of Korea.
Ruthenium (Ru)-based electrocatalysts have shown promise for anion exchange membrane water electrolysis (AEMWE) due to their ability to facilitate water dissociation in the hydrogen evolution reaction (HER). However, their performance is limited by strong hydrogen binding, which hinders hydrogen desorption and water re-adsorption. This study reports the development of RuNi nanoalloys supported on MoO, which optimize the hydrogen binding strength at Ru sites through modulation by adjacent Ni atoms.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
UESTC: University of Electronic Science and Technology of China, School of Materials and Energy, Chengdu, Sichuan, 611731, Chengdu, CHINA.
The electrochemical reduction of carbon dioxide (CO2) to methane (CH4) presents a promising solution for mitigating CO2 emissions while producing valuable chemical feedstocks. Although single-atom catalysts have shown potential in selectively converting CO2 to CH4, their limited active sites often hinder the realization of high current densities, posing a selectivity-activity dilemma. In this study, we developed a single-atom cobalt (Co) doped copper catalyst (Co1Cu) that achieved a CH4 Faradaic efficiency exceeding 60% with a partial current density of -482.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
School of Environment and Safety Engineering, North University of China, Taiyuan, 030051, China.
The initial decomposition reactions of 1,3,5-trinitrobenzene (TNB), picric acid (PA), 2,4,6-trinitrotoluene (TNT), 2,4,6-trinitroaniline (TNA) and 2,4,6-trinitrophenylmethylnitramine (Tetryl) were studied using ReaxFF-lg molecular dynamics simulations, and the substituent effect on the thermal decomposition behaviours of nitrobenzene compounds was evaluated through the reactant number, initial decomposition pathway, products and cluster analysis. The results show that the introduction of substituents could promote the decomposition of the reactants, increase the frequency of the nitro-nitrito isomerization reaction and intermolecular H or O atom transfer reaction, and reduce the frequency of the direct nitro dissociation reaction. Notably, these effects were most obvious in the case of TNT.
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