A potential source of tropospheric secondary organic aerosol precursors: The hydrolysis of N2O5 in water dimer and small clusters of sulfuric acid

A possible atmospheric source of HNO3: the ammonolysis reaction of t-N2O4 in the presence of water monomer, water dimer, and sulfuric acid

“…In the atmosphere, the hydrolysis of t-N 2 O 4 to produce HONO is the most major loss route of t-N 2 O 4 . 10,11 As a complement to the loss of t-N 2 O 4 , the ammonolysis reaction of t-N 2 O 4 can form HNO 3 , 13 which could be competitive with the main source of HNO 3 , the gas-phase reaction of NO 2 with the hydroxyl (OH) radical 8,14 during the day and the hydrolysis reaction of N 2 O 5 [15][16][17] at night, in polluted areas of NH 3 . The ammonolysis of t-N 2 O 4 (shown in eqn ( 1) and ( 2)) investigated by Lin et al 13 reveals that the energy barrier of the t-N 2 O 4 + NH 3 reaction was determined to be 5.3 kcal mol −1 and the corresponding rate constant at low temperature was not pressure-dependent.…”

“…The ammonolysis of t-N 2 O 4 (shown in eqn ( 1) and ( 2)) investigated by Lin et al 13 reveals that the energy barrier of the t-N 2 O 4 + NH 3 reaction was determined to be 5.3 kcal mol −1 and the corresponding rate constant at low temperature was not pressure-dependent. As far as we know, the effect of neutral and acidic gases on the ammonolysis of t-N 2 O 4 , which plays a signicant catalytic role in hydrogen abstraction reactions, 9,15,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] has not been explored.…”

“…In addition to water monomer, some recent works addressed the potential role of water dimer, 18,41 which may play a signicant catalytic role in hydrogen abstraction reactions because its concentrations can reach 9 × 10 14 mol cm −3 . 42,43 Aside from water monomer and water dimer, acidic 9,15,[30][31][32][33][34][35][36][37] gas species in the atmosphere may also be effective in lowering the energy barriers for hydrogen transfer reactions [30][31][32][33][34] and atmospheric hydrolysis reactions 9,15,[35][36][37] in the gas phase. The presence of H 2 SO 4 37,44 in the atmosphere was considered to be a more effective catalyst than neutral catalysts, 25,[28][29][30]33,45 which not only greatly reduces the energy barriers 27,28,33 but also facilitates the transfer of hydrogen, [30][31][32][33]46 In this work, using global minimum searching combined with quantum chemical methods, we rst obtained the stable structures of the reactant complexes of t-N 2 O 4 /NH 3 /X (X = H 2 O, (H 2 O) 2 , and H 2 SO 4 ).…”