The gas-phase infrared spectra of discrete uranyl ([UO2]2+) complexes ligated with acetone and/or acetonitrile were used to evaluate systematic trends of ligation on the position of the O=U=O stretch and to enable rigorous comparison with the results of computational studies. Ionic uranyl complexes isolated in a Fourier transform ion cyclotron resonance mass spectrometer were fragmented via infrared multiphoton dissociation using a free electron laser scanned over the mid-IR wavelengths. The asymmetric O=U=O stretching frequency was measured at 1017 cm(-1) for [UO2(CH3COCH3)2]2+ and was systematically red shifted to 1000 and 988 cm(-1) by the addition of a third and fourth acetone ligand, respectively, which was consistent with increased donation of electron density to the uranium center in complexes with higher coordination number. The values generated computationally using LDA, B3LYP, and ZORA-PW91 were in good agreement with experimental measurements. In contrast to the uranyl frequency shifts, the carbonyl frequencies of the acetone ligands were progressively blue shifted as the number of ligands increased from two to four and approached that of free acetone. This observation was consistent with the formation of weaker noncovalent bonds between uranium and the carbonyl oxygen as the extent of ligation increases. Similar trends were observed for [UO2(CH3CN)n]2+ complexes, although the uranyl asymmetric stretching frequencies were greater than those measured for acetone complexes having equivalent coordination, which is consistent with the fact that acetonitrile is a weaker nucleophile than is acetone. This conclusion was confirmed by the uranyl stretching frequencies measured for mixed acetone/acetonitrile complexes, which showed that substitution of one acetone for one acetonitrile produced a modest red shift of 3-6 cm(-1).

The formation of adduct ions consisting of uranium oxycations and water was studied using an ion trap-secondary ion mass spectrometer. The U(IV) and U(V) species [UO(OH)]+ and [UO2]+ were produced by bombarding the surface of UO3 using molecular primary ions, and the U(VI) species [UO2(OH)]+ was generated by O2 oxidation of [UO(OH)]+ in the gas phase. All three ions formed H2O adducts by termolecular association reactions:  [UO(OH)]+ (a U(IV) species) added three water molecules, for a total of five ligands; [UO2]+ (U(V)) added three or four water molecules, for a total of five or six ligands; and [UO2(OH)]+ (U(VI)) added four water molecules for a total of six ligands. Addition of a seventh ligand was not observed in any of the systems. These analyses showed that the optimum extent of ligation increased with increasing oxidation state of the uranium metal. Hard kinetic models were fit to the time-dependent mass spectral data using adaptive simulated annealing (ASA) to estimate reaction rates and rate constants from kinetic data sets. The values determined were validated using stochastic kinetic modeling and resulted in rate data for all forward and reverse reactions for the ensemble of reactive ions present in the ion trap. A comparison of the forward rate constants of the hydration steps showed that in general, formation of the monohydrates was slow, but that hydration efficiency increased upon addition of the second H2O. Addition of the third H2O was less efficient (except in the case of [UO2]+), and addition of the fourth H2O was even more inefficient and did not occur at all in the [UO2(OH)]+ system. Reverse rate constants also decreased with increasing ligation by H2O, except in the case of [UO(OH)(H2O)4]+, which prefers to quickly revert to the trihydrate. These findings indicate that stability of the hydrate complexes [UO y H z (H2O) n ]+ increases with increasing n, until the optimum number of ligands is achieved. The results enable correlation of uranium hydration behavior with oxidation state.