A193Ir Mössbauer study of Pt−Ir catalysts prepared by impregnantion of silica with H2MCl6

The state of iridium on Pt?Ir catalysts prepared by impregnation of amorphous silica with H₂IrCl₆ and H₂PtCl₆ was studied by¹⁹³Ir Mössbauer spectroscopy after different steps of preparation. The Ir is adsorbed in its trivalent state, presumably as [IrCl₆]^3?. Calcination in air at 450°C converts this to IrO₂. The metallic clusters formed by subsequent reduction in H₂ at 200°C show a strong tendency towards segregation of Ir and Pt and re-oxidize partially when exposed to air at ambient temperature. In both respects the behaviour is similar to that of samples prepared by co-exchange from [Ir(NH₃)₅Cl]Cl₂ and Pt(NH₃)₄Cl₂. H₂O.     

Statistical mechanics of probabilistic cellular automata

We investigate the behavior of discrete-time probabilistic cellular automata (PCA), which are Markov processes on spin configurations on ad-dimensional lattice, from a rigorous statistical mechanics point of view. In particular, we exploit, whenever possible, the correspondence between stationary measures on the space-time histories of PCAs on ^d and translation-invariant Gibbs states for a related Hamiltonian on ( ^d+1). This leads to a simple large-deviation formula for the space-time histories of the PCA and a proof that in a high-temperature regime the stationary states of the PCA are Gibbsian. We also obtain results about entropy, fluctuations, and correlation inequalities, and demonstrate uniqueness of the invariant state and exponential decay of correlations in a high-noise regime. We discuss phase transitions in the low-noise (or low-temperature) regime and review Toom's proof of nonergodicity of a certain class of PCAs.     

Photolysis of hexamethyldisilane at 206 nm

The photolysis of Me₆Si₂ at 206 nm results in two main decomposition processes: simple Si---Si bond breaking with a quantum yield of Φ = 0.21 ± 0.03, and Me₃SiH elimination with the concomitant formation of Me₂SiCH₂ with Φ = 0.18 ± 0.01. There is also a minor decomposition channel with a very small quantum yield, Φ = (5.6 ± 0.2) × 10⁻³, which results in the formation of Me₄Si and Me₂Si. The main fate of the excited Me₆Si₂ molecule produced during photolysis is stabilization by collisional deactivation. The end products observed indicate that the reaction pathways followed by the main intermediates, Me₃Si and Me₂SiCH₂, are the same as those found in the photolysis of Me₄Si (Ahmed et al., J. Photochem. Photobiol. A: Chem. 86 (1995) 33).