The favorable routes for the hydrolysis of CH2OO with (H2O)n (n = 1–4) investigated by global minimum searching combined with quantum chemical methods

Abstract

The hydrolysis reaction of CH₂OO with water and water clusters is believed to be a dominant sink for the CH₂OO intermediate in the atmosphere. However, the favorable route for the hydrolysis of CH₂OO with water clusters is still unclear. Here global minimum searching using the Tsinghua Global Minimum program has been introduced to find the most stable geometry of the CH₂OO⋯(H₂O)_n (n = 1–4) complex firstly. Then, based on these stable complexes, favorable hydrolysis of CH₂OO with (H₂O)_n (n = 1–4) has been investigated using the quantum chemical method of CCSD(T)-F12a/cc-pVDZ-F12//B3LYP/6-311+G(2d,2p) and canonical variational transition state theory with small curvature tunneling. The calculated results have revealed that, although the contribution of CH₂OO + (H₂O)₂ is the most obvious in the hydrolysis of CH₂OO with (H₂O)_n (n = 1–4), the hydrolysis of CH₂OO with (H₂O)₃ is not negligible in atmospheric gas-phase chemistry as its rate is close to the rate of the CH₂OO + H₂O reaction. The calculated results also show that, in a clean atmosphere, the CH₂OO + (H₂O)_n (n = 1–2) reaction competes well with the CH₂OO + SO₂ reaction at 298 K when the concentrations of (H₂O)_n (n = 1–2) range from 20% relative humidity (RH) to 100% RH, and SO₂ is 2.46 × 10¹¹ molecules per cm³. Meanwhile, when the RH is higher than 40%, it is a new prediction that the CH₂OO + (H₂O)₃ reaction can also compete well with the CH₂OO + SO₂ reaction at 298 K. Besides, Born–Oppenheimer molecular dynamics simulation results show that all the favorable channels of the CH₂OO + (H₂O)_n (n = 1–3) reaction cannot react on a time scale of 100 ps in the NVT simulation. However, the NVE simulation results show that the CH₂OO + (H₂O)₃ reaction can be finished well at 8.5 ps, indicating that the gas phase reaction of CH₂OO + (H₂O)₃ is not negligible in the atmosphere. Overall, the present results have provided a definitive example of how the favorable hydrolysis of important atmospheric species with (H₂O)_n (n = 1–4) takes place, which will stimulate one to consider the favorable hydrolysis of water and water clusters with other Criegee intermediates and other important atmospheric species.