In-situ discrimination of the water cluster size distribution in aqueous solution by ToF-SIMS

The size distribution and molecular structure of water clusters play a critical role in the chemical, biological and atmospheric process. The common experimental study of water clusters in aqueous solution is challenged due to the influence of local Hbonding environments on vibration spectroscopies or vacuum requirements for most mass spectrometry technologies. Here, the time-of-flight secondary ion mass spectrometry (ToF-SIMS) combining with a microfluidic chip has been applied to achieve the in-situ discrimination of the size distribution for water clusters in liquid water at room temperature. The results demonstrated that the presented method is highly system stable, reproducible and accurate. The comparison of heavy water with pure water was made to further demonstrate the accuracy of this technique. These results showed that (H 2 O) 3 H + and (D 2 O) 4 D + are the most dominant clusters in pure and heavy water, respectively. This one water molecule difference in the dominant cluster size may due to the nuclear quantum effects on water’s hydrogen bonded network. It is the first time to experimentally show the size distribution of water clusters over a wide range ( n =1–30) for pure (H 2 O) and heavy (D 2 O) water from molecular level. This technique provides an achievable method for liquid water, which offers a bridge to close the gap between theoretical and experimental study of water cluster in aqueous solution.