Abstract
A novel application of desorption/ionization methods of mass spectrometry, e. g. plasma desorption mass spectrometry (PDMS), is the analysis of both the composition and structure of solid materials in one experiment. Cluster ions emitted from the impact of a 252Cf fission fragment on a surface may represent a "view" of the solid construction over atomic distances if composed of atoms from adjacent sites in the surface. A clearer understanding of the mechanism of secondary cluster ion formation is necessary to evaluate the usefulness of PDMS as a surface characterization technique. The aim of this research was to use metal acetate samples to study secondary cluster ion formation in PDMS. In two sets of experiments, metal acetates from period IV and group IIB of the periodic table were used to measure the influence on cluster formation by the ground state electronic configuration and the ionic size, respectively, of the metal constituent. Relative yields for homologous negative and positive secondary cluster ions were determined and compared to thermochemical properties of the metal ion or the metal acetate molecule (AHf and lattice energy). Secondary ions in negative PDMS mass spectra attributable to a gas phase recombination formation mechanism follow trends predicted by these thermochemical properties. Another series of cluster ions, however, with the composition [M(Ac)2]Ac-(where Ac = acetate) does not follow the same trends, indicating possible formation via intact emission from the solid surface. Positive secondary cluster ions showed differences from the negative ions both in the relative yield distribution and the types of ions observed. Positive cluster ions from metal acetates from the fourth period of the periodic table were mainly metal oxides. On the other hand, positive clusters ions from the group IIB of the periodic table were mainly mirror images of the negative spectra. These differences suggest that the bonding characteristics of the metal ion play an important role in the secondary cluster ion formation process.
Mendez Silvagnoli, Winston Reinaldo (1995). A study of the formation of cluster ions from metal acetates using plasma desorption mass spectrometry. Master's thesis, Texas A&M University. Available electronically from
https : / /hdl .handle .net /1969 .1 /ETD -TAMU -1995 -THESIS -M466.