Evidence for the co-existence of isomers of water dimer radical cations and their inter-conversion in a linear ion trap

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 H(2)O(•+) signal profiles and the H(3)O(+) 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.