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Title: Charge transfer initiated nitroxyl chemistry on free silver clusters Ag{sub 2-5}{sup-} : size effects and magic complexes.

Abstract

The reactivity of small silver cluster anions Ag{sub 2--5}- toward nitric oxide and mixtures of nitric oxide with carbon monoxide is investigated under multi-collision conditions in a radio frequency octopole ion trap at temperatures of 100 and 300 K. A strongly cluster size dependent reaction behavior is observed, where reactive fragmentation dominates for clusters with four or fewer atoms and only Ag{sub 5}- is able to form reaction products without dissociation of the metal cluster. The decisive role of charge transfer in the NO bond breakage, NO oxidation, and the formation of free NO{sub 2}{sup -} and N{sub 2}O{sub 4}{sup -} ions, as well as NxO(y>x)-ligands on the silver clusters is discussed. The mass spectrometric data reveal the particular stability of the reaction products AgN{sub 2}O{sub 4}{sup -} and Ag{sub 3}NO{sup -}. The reaction product mass spectra obtained for Ag{sub 5}{sup -} in the presence of NO and CO show the depletion of the NxO(y>x)-ligands on the metal cluster possibly involving the oxidation of CO to CO2.

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
915004
Report Number(s):
ANL/CHM/JA-59134
Journal ID: ISSN 0168-1176; IJMPDN; TRN: US200817%%56
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Intl. J. Mass Spect.
Additional Journal Information:
Journal Volume: 261; Journal Issue: 2007; Journal ID: ISSN 0168-1176
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBON MONOXIDE; MASS SPECTRA; NITRIC OXIDE; OXIDATION; SILVER; ELECTRON TRANSFER; ACTIVATION ENERGY; FRAGMENTATION; CHEMICAL REACTION KINETICS

Citation Formats

Hagen, J, Socaciu-Sieberg, L D, LeRoux, J, Popolan, D, Vajda, S, Bernhardt, T M, Woste, L, Chemistry, Freie Univ., and Univ. Ulm. Charge transfer initiated nitroxyl chemistry on free silver clusters Ag{sub 2-5}{sup-} : size effects and magic complexes.. United States: N. p., 2007. Web. doi:10.1016/j.ijms.2006.08.008.
Hagen, J, Socaciu-Sieberg, L D, LeRoux, J, Popolan, D, Vajda, S, Bernhardt, T M, Woste, L, Chemistry, Freie Univ., & Univ. Ulm. Charge transfer initiated nitroxyl chemistry on free silver clusters Ag{sub 2-5}{sup-} : size effects and magic complexes.. United States. https://doi.org/10.1016/j.ijms.2006.08.008
Hagen, J, Socaciu-Sieberg, L D, LeRoux, J, Popolan, D, Vajda, S, Bernhardt, T M, Woste, L, Chemistry, Freie Univ., and Univ. Ulm. 2007. "Charge transfer initiated nitroxyl chemistry on free silver clusters Ag{sub 2-5}{sup-} : size effects and magic complexes.". United States. https://doi.org/10.1016/j.ijms.2006.08.008.
@article{osti_915004,
title = {Charge transfer initiated nitroxyl chemistry on free silver clusters Ag{sub 2-5}{sup-} : size effects and magic complexes.},
author = {Hagen, J and Socaciu-Sieberg, L D and LeRoux, J and Popolan, D and Vajda, S and Bernhardt, T M and Woste, L and Chemistry and Freie Univ. and Univ. Ulm},
abstractNote = {The reactivity of small silver cluster anions Ag{sub 2--5}- toward nitric oxide and mixtures of nitric oxide with carbon monoxide is investigated under multi-collision conditions in a radio frequency octopole ion trap at temperatures of 100 and 300 K. A strongly cluster size dependent reaction behavior is observed, where reactive fragmentation dominates for clusters with four or fewer atoms and only Ag{sub 5}- is able to form reaction products without dissociation of the metal cluster. The decisive role of charge transfer in the NO bond breakage, NO oxidation, and the formation of free NO{sub 2}{sup -} and N{sub 2}O{sub 4}{sup -} ions, as well as NxO(y>x)-ligands on the silver clusters is discussed. The mass spectrometric data reveal the particular stability of the reaction products AgN{sub 2}O{sub 4}{sup -} and Ag{sub 3}NO{sup -}. The reaction product mass spectra obtained for Ag{sub 5}{sup -} in the presence of NO and CO show the depletion of the NxO(y>x)-ligands on the metal cluster possibly involving the oxidation of CO to CO2.},
doi = {10.1016/j.ijms.2006.08.008},
url = {https://www.osti.gov/biblio/915004}, journal = {Intl. J. Mass Spect.},
issn = {0168-1176},
number = 2007,
volume = 261,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}