Salt cluster ions of alkali metal chlorides AC1 (A = Li+, Na+, K+, Rb+ and Cs+) and sodium salts NaB (B = I-, HCOO-, CH3COO-, NO2-, and NO3-), formed by electrospray ionization, were studied systematically by mass spectrometry. The influences on the total positive ion and negative ion currents of variation of solvent, solution concentration, desolvation temperature, solution flow-rate, capillary voltage and cone voltage were investigated. Only cone voltage was found to influence dramatically the distribution of salt cluster ions in the mass spectra observed. Under conditions of normal cone voltage of Ο70 V, cluster ions having magic numbers of molecules are detected with high relative signal intensity. Under conditions of low cone voltage of Ο10 V, the distribution of cluster ions detected is characterized by a relatively low average mass/charge ratio due to the presence of multiply charged cluster ions; in addition, there is a marked reduction in cluster ions having a magic number of molecules. Product ion mass spectra obtained by tandem mass spectrometry of cluster ions are characterized by a base peak having a magic number of molecules that is less than and closest to the number of molecules in the precursor ion. Structures have been proposed for some dications and some quadruply charged ions. At pH 3 and 11, the mass spectra of NaC1 clusters show the presence of mixed clusters of NaC1 with HC1 and NaOH, respectively. The effects of ionic radius on 20 distributions of cluster ions for 10 salts were investigated; however, the fine structure of these effects is not readily discerned.

Collision-induced dissociation, Electrospray ionization, Multiply charged ion, Salt cluster, Singly charged ion
Journal of Mass Spectrometry
Department of Chemistry

Hao, C. (Chunyan), March, R.E. (Raymond E.), Croley, T.R. (Timothy R.), Smith, J. C, & Rafferty, S.P. (Steven P.). (2001). Electrospray ionization tandem mass spectrometric study of salt cluster ions. Part 1 - Investigations of alkali metal chloride and sodium salt cluster ions. Journal of Mass Spectrometry, 36(1), 79–96. doi:10.1002/jms.107