- Kinetic study of the recombination reaction of gas phase Pd(a1S0) with O2 from 294 to 523 K
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The gas-phase removal rate constants for the reaction of ground-state palladium (a1S0) with oxygen in argon buffer are reported as a function of temperature and pressure. Palladium atoms were produced by the photodissociation of palladium(II) trifluoroacetate and detected by laser-induced fluorescence. The reaction is pressure dependent, indicating recombination to form PdO2. Falloff behavior is observed at pressures above about 20 Torr. Quantum calculations indicate that the reaction proceeds on a triplet surface to form bent PdO2(3A″), which has a low frequency bending mode of only 129 cm-1 and a bond energy D0 = 95 kJ mol-1. RRKM theory, fitted to the experimental data, shows that D0 should lie below 155 kJ mol-1 and predicts the following expression for the rate coefficient from 200 to 600 K: krec,0 = 1.09 × 10-30 (T/300 K)-2.76 cm6 molecule-2 s-1, krec,∞ = 2.52 × 10-10 exp(-69.3/T) cm3 molecule-1 s-1, and Fc = 0.61.
- Campbell, Mark L.,Plane, John M. C.
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- Precious metal-molecular oxygen complexes: Neon matrix infrared spectra and density functional calculations for M(O2), M(O2)2 (M = Pd, Pt, Ag, Au)
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Laser-ablated palladium, platinum, silver, and gold atoms react with molecular oxygen in excess neon during condensation at 4 K. Reaction products, M-(η2-OO), M-(η2-OO)2 (M = Pd, Pt), PtO, PtO2, AuO2,
- Wang, Xuefeng,Andrews, Lester
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p. 5812 - 5822
(2007/10/03)
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