Reactions of pulsed-laser evaporated uranium atoms with molecular oxygen: Infrared spectra of UO, UO2, UO3, UO2+, UO22+, and UO3–O2 in solid argon

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Abstract
Uranium atoms from the Nd:YAG laser ablation of a uranium target were codeposited with molecular oxygen and excess argon at 12 K. Infrared spectra following the U+O2 reaction revealed a wide range of reaction products. The 776.0 cm−1 band due to UO2 was the strongest product absorption, strong UO3 bands were observed at 852.5 and 745.5 cm−1, and a weak UO absorption appeared at 819.8 cm−1. These product absorptions are in agreement with earlier work, which evaporated UO2 from a tungsten Knudsen cell at 2000 °C. The 16O2/18O2 reaction gave only U 16O2 and U 18O2, which verified an insertion mechanism. New product absorptions were observed at 952.3, 892.3, and 842.4 cm−1. The 842.4 cm−1 absorption due to the UO3–O2 complex and the 892.3 cm−1 band assigned to the charge-transfer complex (UO2+)(O2−) grew markedly at the expense of the other uranium oxides during annealing the matrix to allow diffusion and reaction of O2. With 25% 16O2, 50% 16O18O, and 25% 18O2 samples, the 952.3 cm−1 band became a sharp triplet at 952.3, 936.5, and 904.5 cm−1 and exhibited an isotopic ratio appropriate for a linear OUO species. Agreement of this band with uranyl ion spectra suggests assignment to a (UO22+) complex. Mechanisms of formation of charged species are discussed.