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Three oxygen-containing gas-phase diatomic trications ReO(3+), NbO(3+) and HfO(3+) as well as the diatomic tetracation NbO(4+) have been observed by mass spectrometry at non-integer m/z values. These unusual triply charged molecular ion species, together with the corresponding diatomic dications ReO(2+), NbO(2+) and HfO(2+), were produced by energetic, high-current oxygen ((16)O(-)) ion beam sputtering of rhenium, niobium and hafnium metal samples, respectively, whose surfaces were dynamically oxidized by oxygen primary ion incorporation. In addition, NbO(z+) (z≤ 4) were generated by intense femtosecond laser excitation and photofragmentation (Coulomb explosion) of Nb(x)O(y) clusters and were detected through Time-of-Flight Mass Spectrometry (TOF). Our experimental results confirm previous reports on the detection of NbO(4+), NbO(3+), NbO(2+), HfO(3+) and HfO(2+) with Atom Probe mass spectrometry, whereas ReO(3+) and ReO(2+) apparently had not been observed before. In addition, these multiply charged molecular ions have been studied theoretically for the first time. Ab initio calculations of their electronic structures show that the diatomic trications ReO(3+), NbO(3+) and HfO(3+) are long-lived metastable gas-phase species, with bond lengths of 1.61 Å, 1.62 Å and 1.86 Å, respectively. They present large potential barriers with respect to dissociation of more than 2.7 eV. The corresponding diatomic dications are thermochemically stable molecules with very large dissociation energies (>3.5 eV). Our calculations predict the diatomic tetracation ReO(4+) to be a metastable ion species in the gas phase. We compute a potential barrier toward fragmentation of 0.6 eV; its formation requires a quadruple adiabatic ionization energy of 85.7 eV. Even though our calculations show that NbO(4+) is a weakly bound (dissociation barrier ∼0.1 eV) metastable molecule, it is here identified via linear time-of-flight mass spectrometry.

Massive cluster impact (MCI) combined with microscope-mode ion imaging allows rapid imaging using ionized intact biomolecules, with a lateral resolution acceptable for applications with biological samples.

We have extended our previous experiment [Schauer et al., Phys. Rev. Lett. 65, 625 (1990)] where we had produced small gas-phase dianion clusters of C(n) (2-)(n > or =7) by means of sputtering a graphite surface by Cs(+) ion bombardment. Our detection sensitivity for small C(n) (2-) could now be increased by a factor of about 50 for odd n. Nevertheless, a search for the elusive pentamer dianion of C(5) (2-) was not successful. As an upper limit, the sputtered flux of C(5) (2-) must be at least a factor of 5000 lower than that of C(7) (2-), provided that the lifetime of C(5) (2-) is sufficiently long to allow its detection by mass spectrometry. When oxygen gas (flooding with either O(2) or with N(2)O) was supplied to the Cs(+)-bombarded graphite surface, small dianions of OC(n) (2-)(5< or =n < or =14) and O(2)C(7) (2-) were observed in addition to C(n) (2-)(n > or =7). Similarly, Cs(+) sputtering of graphite with simultaneous SF(6) gas flooding produced SC(n) (2-)(6< or =n< or =18). Mixed nitrogen-carbon or fluorine-carbon dianion clusters could not be observed by these means. Attempts to detect mixed metal-fluoride dianions for SF(6) gas flooding of various Cs(+)-bombarded metal surfaces were successful for the case of Zr, where metastable ZrF(6) (2-) was observed. Cs(+) bombardment of a silicon carbide (SiC) wafer produced SiC(n) (2-) (n=6,8,10). When oxygen gas was supplied to the Cs(+)-bombarded SiC surface, small dianions of SiOC(n) (2-) (n=4,6,8) and of SiO(2)C(n) (2-) (n=4,6) as well as a heavier unidentified dianion (at mz=98.5) were observed. For toluene (C(7)H(8)) vapor flooding of a Cs(+)-bombarded graphite surface, several hydrocarbon dianion clusters of C(n)H(m) (2-)(n> or =7) were produced in addition to C(n) (2-)(n> or =7), while smaller C(n)H(m) (2-) with n< or =6 could not be observed. BeC(n) (2-) (n=4,6,8,10), Be(2)C(6) (2-), as well as BeC(8)H(m) (2-) (with m=2 and/or m=1) were observed for toluene vapor flooding of a Cs(+)-bombarded beryllium metal foil. The metastable pentamer (9)Be(12)C(4) (2-) at mz=28.5 was the smallest and lightest dianion molecule that we could detect. The small dianion clusters of SC(n) (2-), OC(n) (2-), BeC(n) (2-), and SiO(m)C(n) (2-) (m=0,1,2) have different abundance patterns. A resemblance exists between the abundance patterns of BeC(n) (2-) and SiC(n) (2-), even though calculated molecular structures of BeC(6) (2-) and SiC(6) (2-) are different. The abundance pattern of SC(n) (2-) is fairly similar to that of C(n) (2-).