In the present work, we investigated the influence of water on the gas-phase reaction of formaldehyde (HCHO) with hydroperoxyl radicals () using quantum chemical calculations and kinetics. For quantum chemical calculations, we used the CCSD(T)-F12/cc-pVTZ-F12//M06-2X/6-311+G(2df,2p) level of theory, while for the rate constant calculation, we used conventional transition state theory. Our study suggests that the water catalyzed HCHO path proceeds much slower than the uncatalyzed reaction over the temperature range 200-450 K. By comparing the rate constant of water catalyzed HCHO with the water catalyzed HCHO reaction, we found that cannot compete with in degrading HCHO in the presence of water.Graphical abstract Water signifi cantly suppresses the reactions of HCHO with both HO and HO radicals. However, the inhibition is much stronger for HCHO + HO than for the HCHO + HO reaction, indicating HO is not a significant sink for HCHO in the atmosphere and humid conditions.
A [Cu]-catalyzed cascade reaction involving self-condensation and cyclization of tert-propargylic alcohols affording 1H-cyclopenta[b]naphthalenes and dihydro-indenopyrans has been developed. While the 2-methyl substituted propargylic alcohols led to 1H-cyclopenta[b]naphthalenes, 2-diaryl substituted propargylic alcohols furnished dihydro-indenopyrans in moderate to good yields. The transformation proceeded under mild conditions using Cu(OTf)2 and p-toluenesulfonic acid (p-TsOH) as cooperative catalysts. The scope, mechanism, and synthetic potential of this cyclization are discussed.Graphical abstract Tert-propargyl alcohols bearing a 2-methyl or 2-diaryl group undergo self-condensation to afford cyclopenta[b]naphthalenes or dihydro-indenopyrans.
In the last few decades, first principle based beyond Born–Oppenheimer (BBO) theory has been developed and widely applied for several molecular species of spectroscopic interest, triatomic reactive scattering processes as well as unit cells of solid crystals, where adiabatic potential energy surfaces (PESs) and non-adiabatic coupling terms (NACTs) appear as real-valued functions. On the other hand, in our recent work (J. Chem. Theory Comput., 2025, 21, 10166–10176), Complex BBO (CBBO) theory has been introduced to investigate the functional forms of complex mixing angles for Jahn–Teller (JT) distortion phenomenon vis-á-vis such theory has been employed on a benchmark molecular system of spectroscopic interest, benzene radical cation (C _6 H _6^+ ). It is worth mentioning that, apart from the JT phenomenon, formulation of CBBO theory is indeed necessary for correct description of electron–nuclear couplings for two important phenomena/properties, namely, (a) complex absorbing potential and radioactivity, and (b) spin–orbit couplings. In order to construct diabatic Hamiltonian for such cases, earlier developed CBBO theory is extended in the present work. For case (a), adiabatic PESs are complex, but NACTs are real, whereas reverse situation originates for case (b) involving real adiabatic PESs and complex electron–nuclear couplings due to imaginary components of spin–orbit coupling terms. The graphical abstract represents expressions of diabatic potential energy surfaces (PESs) and couplings for a system with two coupled electronic states for two different cases: complex adiabatic PESs matrix with real electron-nuclear couplings as well as real adiabatic PESs matrix with complex electron-nuclear (spin-orbit) couplings.
Constructing efficient sodium-ion batteries is of extremely important strategic significance for the green transformation of the global energy structure. In order to promote the innovative breakthroughs of high-performance anode materials for sodium-ion batteries, this study uses the calculation method of density functional theory (DFT) to systematically explore and analyze the spatial configurations, electronic energy band structures, and reversible sodium storage performances of pure C60 fullerenes, a series of C59X (where X represents B, N, P, Si elements) derivatives doped with heteroatoms, and the intercalation complexes with sodium ions (including two systems: Na@C59X and Na+@C59X). B and N doping cause minor structural changes, while P and Si induce significant cage distortion due to their larger atomic radii. Doping generally reduces the HOMO–LUMO gap, enhancing conductivity, with the N-doped system showing the smallest gap (1.89 eV). Sodium embedding further tunes the electronic structure. All dopants increase the binding-energy voltage in sodium-embedded systems, with boron having the strongest effect (binding energy, −66.15 kcal·mol–1; cell voltage, −1.13 V). These results reveal a synergistic mechanism between heteroatom doping and sodium intercalation, providing theoretical guidance for designing advanced anode materials. synopsis How can we make sodium-ion batteries more powerful? Boron doping of buckyballs (C60) is shown to create aneffi cient trap for sodium ions, leading to a signifi cant enhancement in battery voltage and stability. This molecular-scale design strategy presents a promising avenue for the development of sustainable, high-performance energystorage materials
By freezing a class of heavy, deformed molecules to the brink of absolute zero, scientists are developing promising systems for precision measurements that hold great significance in quantum sensing and metrology, providing a powerful tool for exploring their use in fundamental physics. Hutzler and co-workers recently demonstrated the production and cryogenic cooling of radioactive molecules, namely RaF, RaOH and RaOD, using a compact tabletop apparatus (Conn C J et al. 2026 Science 393 319–323). This achievement opens new avenues for combining high-fidelity metrology and quantum probing protocols for short-lived radioactive molecules, offering new opportunities to track down fundamental physics beyond the Standard Model. Cryogenic cooling of short-lived radioactive molecules containing pear-shaped radium nuclei opens new opportunities for quantum sensing and metrology.
