Trapping and Structural Characterization of the XNO2·NO3– (X = Cl, Br, I) Exit Channel Complexes in the Water-Mediated X– + N2O5 Reactions with Cryogenic Vibrational Spectroscopy
| Autor: | Patrick J. Kelleher, Mark A. Johnson, Fabian S. Menges, Barak Hirshberg, Gary H. Weddle, Joanna K. Denton, Joseph W. DePalma, Robert Benny Gerber |
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| Rok vydání: | 2017 |
| Předmět: |
010504 meteorology & atmospheric sciences
Chemistry Analytical chemistry Halide Infrared spectroscopy 010402 general chemistry 01 natural sciences 0104 chemical sciences Ion Yield (chemistry) Cluster (physics) Molecule Physical chemistry General Materials Science Ion trap Physical and Theoretical Chemistry Stoichiometry 0105 earth and related environmental sciences |
| Zdroj: | The Journal of Physical Chemistry Letters. 8:4710-4715 |
| ISSN: | 1948-7185 |
| DOI: | 10.1021/acs.jpclett.7b02120 |
| Popis: | The heterogeneous reaction of N2O5 with sea spray aerosols yields the ClNO2 molecule, which is postulated to occur through water-mediated charge separation into NO3ˉ and NO2+ followed by association with Clˉ. Here we address an alternative mechanism where the attack by a halide ion can yield XNO2 by direct insertion in the presence of water. This was accomplished by reacting Xˉ(D2O)n (X=Cl, Br, I) cluster ions with N2O5 to produce ions with stoichiometry [XN2O5]ˉ. These species were cooled in a 20 K ion trap and structurally characterized by vibrational spectroscopy obtained using the D2 messenger tagging technique. Analysis of the resulting band patterns with DFT calculations indicates that they all correspond to exit channel ion-molecule complexes based on the association of NO3ˉ with XNO2, with the NO3ˉ constituent increasingly perturbed in the order I>Br>Cl. These results establish that XNO2 can be generated even when more exoergic reaction pathways involving hydrolysis are available, and demonstrate ... |
| Databáze: | OpenAIRE |
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