Ionization of Dichloromethane by a Vacuum Ultraviolet Krypton Lamp: Competition Between Photoinduced Ion-Pair and Photodissociation-Assisted Photoionization

The photodissociation and photoionization behaviors of haloalkanes in the VUV regime are important to fully understand the mechanism of ozone depletion in the stratosphere. The ionization of dichloromethane (CH₂Cl₂) under the irradiation of 10.0 and 10.6 eV light was investigated. CH₂Cl⁺ was observed at 10 Pa, while both CH₂Cl⁺ and CHCl₂⁺ were observed at higher pressure. The production efficiency of CH₂Cl⁺ decreased with the increasing number density of CH₂Cl₂, while that of CHCl₂⁺ increased. A kinetic model was successfully derived to quantitatively describe the variation trends of CH₂Cl⁺ and CHCl₂⁺, in which the competition between photoinduced ion-pair and photodissociation-assisted photoionization (PD-PI) were included. The ion-pair channel was quenched efficiently at higher pressure or concentration, which reduced its contribution. Our study proposed new insights into the complicated photoexcitation behaviors of CH₂Cl₂ in the VUV regime and revealed the important role of photodissociation in photoionization at low photon flux.