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Two five‐coordinate mononuclear DyIII single‐molecule magnets [(TrapenTMS)Dy(L)] (Trapen=tris(2‐aminobenzyl) amine; TMS=SiMe3; L=OPMe31, OPEt32) have been synthesized by the reaction of [(TrapenTMS)Dy(THF)] and OPMe3, OPEt3, respectively. The molecular structures of 1 and 2 were fully established by single crystal X‐ray diffraction. The centre DyIII ions of both complexes exhibit distorted triangular bipyramid geometries, varying with different neutral ligands L on the apex. The TrapenTMS ligand forms the pyramid base of the trigonal bipyramid. Subtle structural modifications of the axial O‐ligand terminal substituent result in different dynamic magnetic behaviors. Magnetic data analysis reveals that 1 and 2 exhibit the characteristic behavior of SMM without a dc field, accompanying an unambiguous quantum tunneling of the magnetization. Field‐induced slow magnetic relaxation was observed for 1 and 2 under an applied bias dc field of 1000 Oe, the relaxation energy barriers are 107 K and 88 K for 1 and 2, respectively. We have investigated the differences in magnetism and magnetic anisotropy between the two complexes by ab initio calculations. [ABSTRACT FROM AUTHOR]

A detailed effects of catalyst X (X = H2O, (H2O)2, NH3, NH3···H2O, H2O···NH3, HCOOH and H2SO4) on the HO4H → O3 + H2O reaction have been investigated by using quantum chemical calculations and canonical vibrational transition state theory with small curvature tunnelling. The calculated results show that (H2O)2-catalysed reactions much faster than H2O-catalysed one because of the former bimolecular rate constant larger by 2.6–25.9 times than that of the latter one. In addition, the basic H2O···NH3 catalyst was found to be a better than the neutral catalyst of (H2O)2. However it is marginally less efficient than the acidic catalysts of HCOOH, and H2SO4. The effective rate constant (k't) in the presence of catalyst X have been assessed. It was found from k't that H2O (at 100% RH) completely dominates over all other catalysts within the temperature range of 280–320 K at 0 km altitude. However, compared with the rate constant of HO4H → H2O + O3 reaction, the keff values for H2O catalysed reaction are smaller by 1–2 orders of magnitude, indicating that the catalytic effect of H2O makes a negligible contribution to the gas phase reaction of HO4H → O3 + H2O. Highlights A detailed effects of catalyst of H2O, (H2O)2, NH3, NH3···H2O, H2O···NH3, HCOOH and H2SO4 on the HO4H → O3 + H2O reaction has been performed. From energetic viewpoint, H2SO4 exerts the strongest catalytic role in HO4H → O3 + H2O reaction as compared with the other catalysts. At 0 km altitude H2O (at 100% RH) completely dominates over all other catalysts within the temperature range of 280–320 K. HO4H → H2O + O3 reaction with H2O cannot be compete with the reaction without catalyst, due to the fact that the effective rate constants in the presence of H2O are smaller. [ABSTRACT FROM AUTHOR]

Hydrolysis of NO 2 dimer is of great interest in atmospheric chemistry because it can form HONO, a major source of OH in polluted urban atmospheres. Herein, the reaction mechanism and kinetics for the hydrolysis of trans -ONONO 2 (the favorable route in the hydrolysis of NO 2 dimer) catalyzed by catalyst X (X = H 2 SO 4 , H 2 SO 4 ⋯ H 2 O, and (H 2 SO 4) 2) have been studied theoretically. The calculated results show that the addition of X not only increases the stabilization energy of the reactant complex, but also decreases the energy barrier by over 7.0 kcal⋅mol−1. Kinetic simulations show that H 2 SO 4 ⋯ H 2 O exerts the strongest catalytic role as compared with H 2 SO 4 , and (H 2 SO 4) 2 with its pseudo-first-order rate constant k t ′ (SW) respectively larger by 6–5 and 10–11 orders of magnitude. Additionally, compared with the rate constant of t -ONONO 2 + H 2 O reaction, the k t ′ (SW) of t -ONONO 2 + H 2 SO 4 ··· (H 2 O) 2 reaction increase by 13 times at 298 K. Therefore, the present work may suggest that formation of nitrous acid from the hydrolysis reaction of t -N 2 O 4 is promoted significantly by pre-existing aerosols of small clusters of sulfuric acid. Image 1 • A catalytic effect of H 2 SO 4 , H 2 SO 4 ⋯ H 2 O and (H 2 SO 4) 2 on the t -ONONO 2 + H 2 O reaction has been investigated. • All of H 2 SO 4 , H 2 SO 4 ⋯ H 2 O and (H 2 SO 4) 2 catalysts can substantially reduce the energy barriers of the reaction. • The H 2 SO 4 ⋯ H 2 O catalyst has the most obvious catalytic effect on the t -ONONO 2 + H 2 O reaction. [ABSTRACT FROM AUTHOR]