The hydrolysis of NO2 dimer in small clusters of sulfuric acid: A potential source of nitrous acid in troposphere

Possible atmospheric source of NH2SO3H: the hydrolysis of HNSO2 in the presence of neutral, basic, and acidic catalysts

“…From an energy point of view, the binding energy of t-H 2 SO 4 Á Á ÁH 2 O was 10.4 kcal mol À1 , which agreed well with the previous reported value 28,33,34 of 10.1 kcal mol À1 . Starting from the HNSO 2 + t-H 2 SO 4 Á Á ÁH 2 O reactants, the stepwise route of Channel SA was initiated by complex IM_SA 0 , where a van der Waals interaction (2.60 Å) was formed between the O atom of the H 2 O moiety in t-H 2 SO 4 Á Á ÁH 2 O and the S atom of HNSO 2 .…”

“…The values in brackets are from experiments. 10,11,21,28,29,33,34,[58][59][60][61][62][63] lengths (Å) and bond angles. [58][59][60][61][62][63] The mean absolute deviation of bond lengths (Å) and bond angles (1) between the calculations at the M06-2X/6-311+G(2df,2pd) level and the experimental values were less than 0.01 Å and 1.61, respectively.…”

“…These geometrical structures were also in good agreement with earlier findings. 21,28,29,33,34,65 The stabilization energies of (…”

“…with respect to the isolated reactants were in the range of À2.5 to À18.3 kcal mol À1 , and these energy values matched well with the earlier findings. 11,19,21,28,29,33,34,66 As for the reactant complexes HNSO 2 Á Á ÁH 2 OÁ Á ÁX, their optimized geometries and stabilization energies are illustrated in Fig. 2.…”

“…At the same time, previous studies [30][31][32] have shown that the bimolecular complexes of H 2 SO 4 Á Á ÁH 2 O and (H 2 SO 4 ) 2 are not only the initial cluster formations of the nucleation process when H 2 SO 4 is involved, but also exist in large quantities in a natural environment. Moreover, these two bimolecular acidic catalysts exhibit obvious catalytic effects in the hydrolysis reactions of COS, 28 SO 2 , 21 CH 2 OO, 33 and N 2 O 4 34 by increasing the stability of the reactant complexes and reducing the reaction energy barriers. These situations stimulated our interest in studying the hydrolysis of HNSO 2 by neutral, basic, and acidic catalysts.…”