Infrared laser single photon absorption reaction chemistry in the solid state. I. The system SiH4–UF6 a)

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Abstract
The reaction between SiH4 and UF6 under thermal gas phase and photon initiated conditions in cryogenic matrices has been investigated. The gas phase thermal reaction begins at 130–140° C producing HF, SiH3F, and a soliduranium fluoride product. When the UF6 is matrix isolated within SiH4 at 12 K and exposed to low power infrared radiation of 25 mW cm−2 using laser emissions resonant with the ν3 band of UF6, a reaction also occurs. This reaction produces SiH3F, UF5, and UF4 as products. The same reaction is also catalyzed using a broad band incoherent source with a photon flux density of 10 μW cm−2. The activation energy for the photoreaction (1.8 kcal mol−1) is considerably lower than the thermal activation barrier for the gas phase reaction. These experiments are part of the bases for uncovering a process of photochemistry of reactants in fixed relative configurations–single photon absorptionreaction chemistry in the solid state (SPARCSS). This process is a manifestation of a previously unrecognized, general matrix phenomenon in which spatial configurations dramatically affect potential energy surfaces for reaction.

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