Reactions of laser-ablated uranium atoms, cations, and electrons with O2 during condensation with excess neon produce UO, UO2, UO3, UO2 +, and UO2 - as characterized by infrared spectra with oxygen isotopic substitution and B3LYP/pseudopotential calculations. Differences in low-lying states for UO2 give rise to substantial shifts and ground state reversal between argon and neon matrices. A series of B3LYP/pseudopotential calculations has been undertaken on oxide species related to the uranyl dication by the addition of one, two, or three electrons. Several electronic states have been characterized for each species. These simple, low-cost calculations predict vibrational frequencies which match those observed in neon matrices extremely well (typically 3−5% too high). The ground state of neutral UO2 appears to have 3Φu symmetry, while 2Φu ground states are implied for UO2 + and UO2 -.

Laser-ablated W atoms react with CH4 in excess argon to form the CH3-WH, CH2=WH2, and CH[triple bond]WH3 molecules with increasing yield in this order of product stability. These molecules are identified from matrix infrared spectra by isotopic substitution. Tungsten methylidene and methylidyne hydride molecules are reversibly interconverted by alpha-H transfers upon visible and ultraviolet irradiations. Matrix infrared spectra and DFT/B3LYP calculations show that CH[triple bond]WH3 is a stable molecule with C3v symmetry, but other levels of theory were required to describe agostic distortion for CH2=WH2. Analogous reactions with Cr gave only CH3-CrH, which is calculated to be by far the most stable product.

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