Campus Units

Chemistry, Ames Laboratory

Document Type

Article

Publication Version

Published Version

Publication Date

3-2008

Journal or Book Title

Journal of Physical Chemistry A

Volume

112

Issue

12

First Page

2610

Last Page

2617

DOI

10.1021/jp077209k

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.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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