Theoretical Investigation of Small Polyatomic Ions Observed in Inductively Coupled Plasma Mass Spectrometry:  HxCO+ and HxN2+ (x = 1, 2, 3)

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2008-03-01
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Sears, Kyle
Ferguson, Jill
Dudley, Timothy
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Houk, Robert
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Ames National Laboratory

Ames National Laboratory is a government-owned, contractor-operated national laboratory of the U.S. Department of Energy (DOE), operated by and located on the campus of Iowa State University in Ames, Iowa.

For more than 70 years, the Ames National Laboratory has successfully partnered with Iowa State University, and is unique among the 17 DOE laboratories in that it is physically located on the campus of a major research university. Many of the scientists and administrators at the Laboratory also hold faculty positions at the University and the Laboratory has access to both undergraduate and graduate student talent.

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Chemistry

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The Department of Chemistry was founded in 1880.

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Abstract

Two series of small polyatomic ions, HxCO+ and HxN2+ (x = 1, 2, 3), were systematically characterized using three correlated theoretical techniques:  density functional theory using the B3LYP functional, spin-restricted second-order perturbation theory, and singles + doubles coupled cluster theory with perturbative triples. On the basis of thermodynamic data, the existence of these ions in inductively coupled plasma mass spectrometry (ICP-MS) experiments is not surprising since the ions are predicted to be considerably more stable than their corresponding dissociation products (by 30−170 kcal/mol). While each pair of isoelectronic ions exhibit very similar thermodynamic and kinetic characteristics, there are significant differences within each series. While the mechanism for dissociation of the larger ions occurs through hydrogen abstraction, the triatomic ions (HCO+ and HN2+) appear to dissociate by proton abstraction. These differing mechanisms help to explain large differences in the abundances of HN2+ and HCO+ observed in ICP-MS experiments.

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Reprinted (adapted) with permission from Journal of Physical Chemistry A 112 (2008): 2610, doi:10.1021/jp077209k. Copyright 2008 American Chemical Society.

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Tue Jan 01 00:00:00 UTC 2008
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