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Determination of dissociation temperature for ArO in inductively coupled plasma-mass spectrometry: Effects of excited electronic states and dissociation pathways
Authors:Sally M McIntyre  Jill Wisnewski Ferguson  RS Houk
Institution:aAmes Laboratory U.S. Department of Energy, Department of Chemistry, Iowa State University, Ames, IA 50011, USA
Abstract:The method of comparing experimental and calculated ion ratios to determine a gas kinetic temperature (Tgas) characteristic of the origin of a polyatomic ion in inductively coupled plasma-mass spectrometry (ICP-MS) is applied to ArO+. Repeated measurements of ion ratios involving this species yield erratic Tgas values. Complications arise from the predicted presence of a low-lying excited electronic state (2Π) above the 4Σ ground state. Omission of this excited state yields unreasonably high temperatures (> 10,000 K) for nine out of nineteen trials. Inclusion of the excited electronic state in the partition function of ArO+ causes temperatures to increase further. The problem appears to be related to the prediction that ArO+ in the 2Π excited state dissociates into Ar+ and O, different products than ArO+ 4Σ which dissociates into Ar and O+. Adjustments to the calculations to account for these different products yield reasonable temperatures (2100 to 3500 K) that are consistent from day-to-day and similar to those seen for other weakly-bound polyatomic ions.
Keywords:Inductively coupled plasma-mass spectrometry  Inductively coupled plasma  Ion extraction  Argon oxide ion: ArO+
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