Au‐induced decomposition of N₂O

Abstract

Reactions between small gold cluster ions, Au 1‐4+, and N2O were studied in a Penning trap mass spectrometer. Gold clusters were produced by laser vaporization and injected into a Penning trap. After reaction times of 50–7000ms the products were detected by time‐of‐flight mass spectrometry. For the major reaction channel, Au 1,2+ + N2O→Au1,2N + NO+, rates of (0.9±0.1)×10−12 cm3 s−1 and (2.4±0.4)×10−12 cm3 s−1 were determined which are about a factor 500 below the collision rate. The corresponding activation energies for N2O decomposition were estimated to lie below 0.6 eV and 0.3 eV. Additional products with small branching ratios were detected, viz. the ions Au1O+, Au1N2O+, Au2N+, Au2NO+, Au2N2O+, Au3O+, Au3N2O+, and Au4N2O+. This indicates a preference for nitrogen‐oxygen bond rupture in the case of Au 1+ and Au 3+, and for nitrogen‐nitrogen bond rupture in the case of Au 2+.

Structural isomers and low-lying electronic states of gas-phase M+(N2O)n (M = Co, Rh, Ir) ion–molecule complexes

“…9 Metal atom-N 2 O binding has been studied both theoretically [10][11][12] and experimentally, 13,14 and the reactions of nitrous oxide with charged metal clusters have received much attention both under thermal and single-collision conditions. [15][16][17][18][19][20][21][22][23] We recently reported a spectroscopic study of M + (N 2 O) n (M = Cu, Ag, Au) complexes in which infrared photodissociation (IRPD) spectroscopy was combined with quantum chemical calculations to identify common structural binding motifs. 24 Spectroscopically distinct nitrogen-and oxygen-bound ligands were identified giving rise to a rich diversity of structural isomers.…”

Infrared Signature of Structural Isomers of Gas–Phase M+(N2O)n (M = Cu, Ag, Au) Ion–Molecule Complexes

“…Clearly, N 2 O can act as both an O and N source for atomic cations, leading to oxide and nitride formation . Theoretical studies of N 2 O interactions with neutral atomic metal centers support O-coordination of N 2 O, − but matrix isolation infrared studies report N-coordination to metal centers such as Ni, Pd, Pt, and MCl (M = Cu, Ag). , The gas-phase reactivity of nitrous oxide with metal ions and clusters has been studied by several groups, − but relevant gas-phase infrared spectroscopy of N 2 O complexes is limited to pure (N 2 O) n ± complexes; , free electron laser studies of N 2 O on Rh n + clusters; − and blackbody infrared radiative dissociation . The studies of N 2 O on metal clusters demonstrated the ability to drive decomposition of the nitrous oxide on size-selected clusters (with resulting N 2 loss) using resonant infrared excitation.…”

Gas Phase Formation, Structure and Reactivity of Gold Cluster Ions

“…The reactions of small gold cluster cation with N 2 O have been studied in an ion-trap mass spectrometer [272]. Au 2 + reacts with N 2 O to yield NO + as the major product (Eq.…”