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

Supplemental Files
Date
2008-03-01
Authors
Houk, Robert
Gordon, Mark
Sears, Kyle
Ferguson, Jill
Dudley, Timothy
Houk, Robert
Gordon, Mark
Major Professor
Advisor
Committee Member
Journal Title
Journal ISSN
Volume Title
Publisher
Altmetrics
Authors
Research Projects
Organizational Units
Ames Laboratory
Organizational Unit
Chemistry
Organizational Unit
Journal Issue
Series
Department
Ames LaboratoryChemistry
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.

Comments

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

Description
Keywords
Citation
DOI
Collections