Sodium doping and reactivity in pure and mixed ice nanoparticles

Doping of clusters by sodium atoms and subsequent photoionization (NaPI) is used as a fragmentation-free cluster ionization method. Here we investigate different cluster su sing NaPI and electron ionization (EI) with a reflectron time-of-flight mass spectrometer (RTOF). The mass spectra of the same clusters ionized by NaPI and EI reveal significant differences which point to Na reactivity in the clusters. First, we discuss mixed XM ·(H2O)N (X = HNO3 ,N 2O) clusters where reactions between Na and molecules X leads to the "cluster invisibility" for the NaPI method. Second, mixed (NH3)M ·(H2O)N clusters are ob- served by both methods, but they reveal different cluster compositions, and the mass spectra suggest that neither the EI nor the NaPI spectrum corresponds exactly to the neutral cluster distribution. Finally, we discuss the reactions of Na in pure water clusters as a function of the number of Na atoms doped into the clusters. In summary, we present experimental evidence that the NaPI method in the present cases does not reveal the size and composition of the neutral clusters. A detailed understanding of Na reactivity in the clusters is needed for its application as a fragmentation-free cluster ionization method. Besides, we introduce the combination of NaPI and EI as a new tool to investigate the sodium reactivity in clusters and aerosol particles.