We report a first principles molecular dynamics (FPMD) study of the structures, acidity constants (pK(a)) and redox potentials (E-0) of uranyl (UO22+) from ambient conditions to 573 K. It is found that UO22+ keeps five coordination up to 573 K whereas UO2+ transforms from 5 to 4-coordinate as temperature increases to 573 K. The FPMD-based vertical energy gap method is used to derive pK(a)s and E(0)s. The method is validated by comparing with available experimental data (for E0 under the ambient conditions and for pKas from ambient conditions to 367 K), with an uncertainty of 1-2 pKa units and 0.2 V for pK(a) and E-0. The encouraging results demonstrate that the method may be used to predict the pH-Eh diagrams of f-block elements under the conditions of hydrothermal solutions. The results show that the acidity constants of uranyl decrease with temperature and are lower than 3.0 when the temperature is above 473 K, indicating that hydrolytic forms are dominant for U(VI) in the near neutral pH range. The reduction potential increases with temperature, indicating that the reduced state is more significant at higher temperatures.
We thank Matthias Krack for supplying us with the pseudopotential and basis sets for U. We acknowledge the National Science Foundation of China (No. 41222015, 41273074, 41572027 and 21373166), Special Program for Applied Research on Super Computation of the NSFC-Guangdong Joint Fund (the second phase), the Foundation for the Author of National Excellent Doctoral Dissertation of PR China (No. 201228), Newton International Fellowship Program and the financial support from the State Key Laboratory at Nanjing University. We are grateful to the High Performance Computing Center of Nanjing University for allowing us to use the IBM Blade cluster system.
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- DENSITY-FUNCTIONAL THEORY
- 1ST-PRINCIPLES MOLECULAR-DYNAMICS
- TRANSITION-METAL CATIONS
- COMPUTATIONAL ELECTROCHEMISTRY
- THERMODYNAMIC PROPERTIES
- HYDROLYSIS CONSTANTS
- CHLORO COMPLEXES