Vibrational and low temperature optical spectra of the uranyl tricarbonato complex [UO2(CO3)3]4−

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Abstract

Diffuse reflectance (20,000–30,000 cm−1) and luminescence (18,000–21,000 cm−1) spectra of polycrystalline Na4[UO2(CO3)3] have been measured in the temperature range of 4.2–300 K; the i.r. (50–2000 cm−1) and Raman (50–2000 cm−1) spectra have been recorded at room temperature. The vibrational spectra exhibit all frequencies expected for a UO2L3 complex of D3h symmetry with bidentate ligands L. The symmetric and asymmetric stretching vibrations of the uranyl ion occur at wave numbers as low as 808 and 843 cm−1, respectively, indicating strong uranium ← carbonate bonding. The diffuse reflectance spectra consist of four overlapping electronic transitions, the lowest one with origin at 20,680 cm−1 is also seen in emission. The absorption bands are assigned to the spin and parity forbidden components of the πu→δu and πu→φu one-electron excitations. From the splitting of the excited configurations π3uδ1u and π3uφ1u the spin-orbit coupling constant is calculated to be ζ = 1750 cm−1. Possible relationships between measurable spectroscopic properties of the uranyl ion and the strength of bonding in the equatorial plane are discussed.

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