Fragmentation pathways of tungsten hexacarbonyl clusters upon electron ionization

Electron ionization of neat tungsten hexacarbonyl (W(CO)₆) clusters has been investigated in a crossed electron-molecular beam experiment coupled with a mass spectrometer system. The molecule is used for nanofabrication processes through electron beam induced deposition and ion beam induced deposition techniques. Positive ion mass spectra of W(CO)₆ clusters formed by electron ionization at 70 eV contain the ion series of the type W(CO)_n⁺ (0 ≤ n ≤ 6) and W₂(CO)_n⁺ (0 ≤ n ≤ 12). In addition, a series of peaks are observed and have been assigned to WC(CO)_n⁺ (0 ≤ n ≤ 3) and W₂C(CO)_n⁺ (0 ≤ n ≤ 10). A distinct change of relative fragment ion intensity can be observed for clusters compared to the single molecule. The characteristic fragmentation pattern obtained in the mass spectra can be explained by a sequential decay of the ionized organometallic, which is also supported by the study of the clusters when embedded in helium nanodroplets. In addition, appearance energies for the dissociative ionization channels for singly charged ions have been estimated from experimental ion efficiency curves.