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Title: Small gas-phase dianions produced by sputtering and gas flooding

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.2136154· OSTI ID:20723269
;  [1]
  1. Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287 (United States)

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

OSTI ID:
20723269
Journal Information:
Journal of Chemical Physics, Vol. 123, Issue 22; Other Information: DOI: 10.1063/1.2136154; (c) 2005 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English