Water radical cations, (H₂O)_n^+•, are of great research interest in both fundamental and applied sciences. Fundamental studies of water radical reactions are important to better understand the mechanisms of natural processes, such as proton transfer in aqueous solutions, the formation of hydrogen bonds and DNA damage, as well as for the discovery of new gas-phase reactions and products. In applied science, the interest in water radicals is prompted by their potential in radiobiology and as a source of primary ions for selective and sensitive chemical ionization. However, in contrast to protonated water clusters, (H₂O)_nH⁺, which are relatively easy to generate and isolate in experiments, the generation and isolation of radical water clusters, (H₂O)_n^+•, is tremendously difficult due to their ultra-high reactivity. This review focuses on the current knowledge and unknowns regarding (H₂O)_n^+• species, including the methods and mechanisms of their formation, structure and chemical properties.

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.

The formation of protonated water-hydrogen clusters, [H ⁺ (H ₂ O) _n ·m(H ₂ )], in an ion trap at room temperature is demonstrated through the association of protonated water clusters H ⁺ (H ₂ O) _n with H ₂ gas, without any cooling necessary.