Catalytic effect of (H₂O)_n (n = 1–3) clusters on the reaction of HNO₂ + HO → H₂O + NO₂ under tropospheric conditions

Abstract

Table S3 The equilibrium constants of the relevant complexes HOH2O, H2OHO, H2OHNO2, HNO2H2O, HNO2(H2O)2, HNO2(H2O)2a, HO(H2O)2, HO(H2O)2a, HNO2(H2O)3, HNO2(H2O)3a, HO(H2O)3, HO(H2O)3a at 240 -325 K. a, b a Equilibrium constants in units of cm 3 molecule -1 .b All equilibrium constants were calculated by using energies computed at the CCSD(T)/aug-cc-pVTZ level and partition functions obtained at the B3LYP/6-311+G(3df,2dp) level. c The concentration of the corresponding complexes at 298 K.•••(H2O)2a 240 5.48×10 -22 5.06×10 -21 2.35×10 -23 8.20×10 -23 1.09×10 -16 6.92×10 -17 250 4.56×10 -22 3.61×10 -21 2.02×10 -23 7.06×10 -23 3.77×10 -17 2.32×10 -17 278 2.97×10 -22 1.61×10 -21 1.43×10 -23 5.00×10 -23 2.92×10 -18 1.68×10 -18 288 2.61×10 -22 1.26×10 -21 1.30×10 -23 4.52×10 -23 1.32×10 -18 7.45×10 -19 298 2.32×10 -22 1.00×10 -21 1.19×10 -23 4.13×10 -23 6.35×10 -19 3.50×10 -19 308 2.08×10 -22 8.08×10 -22 1.09×10 -23 3.80×10 -23 3.20×10 -19 1.73×10 -19 325 1.77×10 -22 5.83×10 -22 9.68×10 -24 3.37×10 -23 1.10×10 -19 5.78×10 -201.89×10 -19 2.03×10 -19 9.58×10 -16 1.41×10 -15 3.81×10 -18 4.26×10 -18 250 9.53×10 -20 1.04×10 -19 3.28×10 -16 4.96×10 -16 1.80×10 -18 2.06×10 -18 278 1.83×10 -20 2.09×10 -20 2.50×10 -17 4.03×10 -17 2.94×10 -19 3.58×10 -19 288 1.10×10 -20 1.28×10 -20 1.13×10 -17 1.86×10 -17 1.68×10 -19 2.09×10 -19 298 6.80×10 -21 8.03×10 -21 5.39×10 -18 9.08×10 -18 9.95×10 -20 1.26×10 -19 308 4.36×10 -21 5.22×10 -21 2.71×10 -18 4.65×10 -18 6.11×10 -20 7.87×10 -20 325 2.18×10 -21 2.67×10 -21 9.31×10 -19 1.64×10 -18 2.86×10 -20 3.79×10 -20

Determination of the influence of water on the SO3 + CH3OH reaction in the gas phase and at the air–water interface

“…For the reaction of MHS formation in the presence of H 2 O and CH 3 OH, the k 0 of Channels MHS_WM and MHS_MO within the altitude range of 0-15 km can be expressed as eqn (10) and (11), respectively, whereas for SA formation, the k 0 of Channels SA_WM and SA_MO are given by eqn (12) and (13), respectively.…”

“…Interestingly, in some gas phase reactions, a single water molecule can act not only as a catalyst, [4][5][6][7][8][9][10][11] but also as a reactant. 5,12,13 For example, in the H 2 OÁ Á ÁHO 2 + SO 3 reaction, 12 a single water molecule can act as a catalyst to form HSO 5 or as a reactant to form H 2 SO 4 and HO 2 .…”

“…Mechanism and rate coefficient for the gas-phase reaction of SO 3 + CH 3 OH with a single water molecule Previous reports4,7,[9][10][11] have proved that the water monomer is the most efficient catalyst among the water monomer, water dimer and water trimer. Thus, only the effect of water monomer was considered in the gas-phase reaction of SO 3 + CH 3 OH.…”

Effect of (H2O)n (n = 1 and 2) on HOCl + Cl reaction

“…Finally, it is worth mentioning that on adding three or more water molecules in the title reaction, the energy barrier of the reaction will decrease. 30,42,43 But, due to the low concentration of water trimers and tetramers it will not effect the kinetics of the title reaction in the atmosphere. Therefore, we have not studied the effect of a water trimer or tetramer on the title reaction.…”

The effects of the gas–liquid interface and gas phase on Cl/ClO radical interaction with water molecules

“…The catalytic effect of (H 2 O) 1-3 clusters on the reaction of HNO 2 and HO has been proved theoretically, although the relative impacts on water dimers and trimers are not apparent like water monomers. 34 Indeed, the study of Cl/ClO radicals with water clusters and droplets is important in atmospheric chemistry. 35 Chlorine radicals contribute to the depletion of the ozone layer, and the presence of water can affect their reactivity.…”