Insights on Clusters Formation Mechanism by Time of Flight Mass Spectrometry. 2. The Case of Acetone-Water Clusters.

This paper is the second of a series dealing with clusters formation mechanism. In part 1, water clusters with the addition of an electrophilic molecule such as ethanol were studied by Time Of Flight Mass Spectrometry (TOFMS). Mass distributions of molecular clusters of ethanol, water and ethanol-water mixed clusters, were obtained by means of two different ionization methods: Electron Ionization (EI) and picosecond laser Photo-Ionization (PI) at a wavelength of 355 nm. In part 2, the same experimental approach was employed to obtain mass spectra of clusters generated by acetone-water binary mixtures with a different composition. Strong dependence of the mass spectra of clusters with EI and PI on the acetone-water mixing ratio was observed. It was shown that the spectral pattern changes gradually and water-rich cluster signals become fainter while acetone-rich cluster signals become more intensive with increasing acetone concentrations from 0.3% to 40%. Owing to the hydrogen bond acceptor character of acetone, its self-association is discouraged with respect to ethanol. The autocorrelation function (AF) was used to analyze the variation of the water clusters composition with the increase of the acetone concentration in terms of fundamental periodicities. However, although acetone and ethanol present a very different hydrogen-bonding ability, similarly to ethanol-water system, in acetone-water system the formation of water-rich clusters and subsequent metastable fragmentation are the dominant process that determine the clusters distribution, irrespective of the ionization process, while the ionization process significantly affects the acetone-rich clusters distribution. Graphical Abstract ᅟ.