Water dimer radical cations are regarded as key intermediates in many aqueous reactions and biochemical processes. However, the structure of the water dimer radical cations, and particularly the inter-conversion between their isomers, remain difficult to investigate experimentally due to their short lifetime and low abundance under ambient conditions. Furthermore, the isomers cannot be distinguished in a full mass spectra. In this study, we report the experimental evidence for the hemi-bonded and proton-transferred isomers of gas-phase water dimer radical cations, and the inter-conversion process between them in a linear ion trap at low pressure and near room temperature. Multiple collisions of isolated water dimer radical cations with He inside the ion trap were systematically investigated; first, under different trapping times (i.e., reaction times) ranging from 0.03 to 800 ms, and then at a very low collision energies ranging from 0.1% to 10% normalized collision energy. The proton-transferred isomers were dominant at shorter trapping times (≤250 ms), while the hemi-bonded isomers were dominant at longer trapping times (250-800 ms). Moreover, the difference in symmetry of the shapes of the H2O•+ signal profiles and the H3O+ signal profiles implied the existence of two kinds of isomers and there were small potential differences between them. Our results also suggested that by tuning the experimental parameters the hemi-bonded isomers would become dominant, which could allow the study of novel chemical reactions involving the hemi-bonded two-center-three-electron (2c-3e) structure in a linear ion trap.
Keywords: Hemi-bonded isomers; Inter-conversion of isomers; Proton-transferred isomers; Water radical cations.
© 2023 The Authors.