Uranyl Carbonate Complexes in Aqueous Solution and Their Ligand NMR Chemical Shifts and ¹⁷O Quadrupolar Relaxation Studied by ab Initio Molecular Dynamics

Dynamic structural effects, NMR ligand chemical shifts, and ¹⁷O NMR quadrupolar relaxation rates are investigated in the series of complexes UO₂²⁺, UO₂(CO₃)₃^4–, and (UO₂)₃(CO₃)₆^6–. Car–Parrinello molecular dynamics (CPMD) is used to simulate the dynamics of the complexes in water. NMR properties are computed on clusters extracted from the CPMD trajectories. In the UO₂²⁺ complex, coordination at the uranium center by water molecules causes a decrease of around 300 ppm for the uranyl ¹⁷O chemical shift. The final value of this chemical shift is within 40 ppm of the experimental range. The UO₂(CO₃)₃^4– and (UO₂)₃(CO₃)₆^6– complexes show a solvent dependence of the terminal carbonate ¹⁷O and ¹³C chemical shifts that is less pronounced than that for the uranyl oxygen atom. Corrections to the chemical shift from hybrid functionals and spin–orbit coupling improve the accuracy of chemical shifts if the sensitivity of the uranyl chemical shift to the uranyl bond length (estimated at 140 ppm per 0.1 Å from trajectory data) is taken into consideration. The experimentally reported trend in the two unique ¹³C chemical shifts is correctly reproduced for (UO₂)₃(CO₃)₆^6–. NMR relaxation rate data support large ¹⁷O peak widths, but remain below those noted in the experimental literature. Comparison of relaxation data for solvent-including versus solvent-free models suggest that carbonate ligand motion overshadows explicit solvent effects

Quadrupolar NMR Relaxation from <i>ab Initio</i> Molecular Dynamics: Improved Sampling and Cluster Models versus Periodic Calculations

Quadrupolar NMR relaxation rates are computed for ¹⁷O and ²H nuclei of liquid water, and of ²³Na⁺, and ³⁵Cl^– in aqueous solution via Kohn–Sham (KS) density functional theory <i>ab initio</i> molecular dynamics (aiMD) and subsequent KS electric field gradient (EFG) calculations along the trajectories. The calculated relaxation rates are within about a factor of 2 of experimental results and improved over previous aiMD simulations. The relaxation rates are assessed with regard to the lengths of the simulations as well as configurational sampling. The latter is found to be the more limiting factor in obtaining good statistical sampling and is improved by averaging over many equivalent nuclei of a system or over several independent trajectories. Further, full periodic plane-wave basis calculations of the EFGs are compared with molecular-cluster atomic-orbital basis calculations. The two methods deliver comparable results with nonhybrid functionals. With the molecular-cluster approach, a larger variety of electronic structure methods is available. For chloride, the EFG computations benefit from using a hybrid KS functional