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

Journal Article · Mon Jan 01 04:00:00 EST 2007 · Intl. J. Mass Spect.

DOI:https://doi.org/10.1016/j.ijms.2006.08.008· OSTI ID:915004

Hagen, J; Socaciu-Sieberg, L D; LeRoux, J; Popolan, D; Vajda, S; Bernhardt, T M; Woste, L

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.

• Research Organization: Argonne National Laboratory (ANL)
• Sponsoring Organization: SC
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 915004
• Report Number(s): ANL/CHM/JA-59134
• Journal Information: Intl. J. Mass Spect., Journal Name: Intl. J. Mass Spect. Journal Issue: 2007 Vol. 261; ISSN 0168-1176; ISSN IJMPDN
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ACTIVATION ENERGY
CARBON MONOXIDE
CHEMICAL REACTION KINETICS
ELECTRON TRANSFER
FRAGMENTATION
MASS SPECTRA
NITRIC OXIDE
OXIDATION
SILVER