Large-scale computational modeling of the chemical behavior of actinide elements at interfaces
EMSL Project ID
29990
Abstract
High performance parallel computational resources and scalable software has enabled computational chemistry to model actinides at various interfaces, in the presence of multiple ligands in solution, and to obtain a basic understanding of actinide sorption and redox behavior in the subsurface as well as in solutions critical to minimize the generation of new radioactive waste from fuel reprocessing. We propose to study the influence of the local environments on sorption, redox mechanisms and oxidation state stability of actinides in solution, especially for nanoparticle and colloid formation, and at solution/mineral interfaces. We believe that computational chemistry methods that integrate electronic structure and classical techniques provide invaluable information that will make currently existing surface complexation and field-scale models more accurate, and will provide critical guidance that could enhance the effectiveness of separations schemes.We propose to study the actinides thorium through curium in their relevant oxidation states: 1) with nitrate, carbonate, sulfate and phosphate aqueous co-contaminants, interacting with mineral interfaces that including magnetite, quartz, and goethite, 2) forming colloidal or nanophase actinide hydroxides, hydrous oxides and oxides in aqueous solution, and 3) incorporated in actinide containing oxides and minerals. We propose to study these systems with atomistic simulations, using quantum and classical mechanical models through molecular dynamics. We will use Gaussian and Car-Parrinello plane-wave density functional theory (DFT) with relativistic scalar and spin-orbit effects, and will properly account for the influence of the local molecular environment by using a variety of methods including solvent reaction fields, explicit inclusion of solvents, and hybrid point-charge models for extended systems. Ab initio and classical molecular dynamics simulations will be performed to obtain a continuous description of the molecular- and meso-scale reactivity and redox behavior of the actinides in ground water conditions and with co-contaminants as well as for models of reprocessing solutions, and to study the properties of colloids and nanoparticles.
Project Details
Project type
Capability Research
Start Date
2008-10-03
End Date
2011-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Atta-Fynn R, EJ Bylaska, GK Schenter, and WA De Jong. 2011. "Hydration Shell Structure and Dynamics of Curium(III) in Aqueous Solution: First Principles and Empirical Studies." Journal of Physical Chemistry A 115(18):4665-4677. doi:10.1021/jp201043f
Aubriet F, JJ Gaumet, WA De Jong, GS Groenewold, AK Gianotto, ME McIIwain, MJ Van Stipdonk, and CM Leavitt. 2009. "Cerium Oxyhydroxide Clusters: Formation, Structure and Reactivity." Journal of Physical Chemistry A 113(22):6239-6252. doi:10.1021/jp9015432
Bylaska EJ, KA Glass, DJ Baxter, SB Baden, and JH Weare. 2010. "Hard scaling challenges for ab initio molecular dynamics capabilities in NWChem: Using 100,000 CPUs per second." Journal of Physics: Conference Series 180(1):, doi:10.1088/1742-6596/180/1/012028.
Bylaska EJ, KL Tsemekhman, SB Baden, JH Weare, and H Jonsson. 2011. "Parallel Implementation of Gamma-Point Pseudopotential Plane-Wave DFT with Exact Exchange." Journal of Computational Chemistry 32(1):54-69.
Cho HM, WA De Jong, and CZ Soderquist. 2010. "Probing the Oxygen Environment in UO22+ by Solid-State O-17 Nuclear Magnetic Resonance Spectroscopy and Relativistic Density Functional Calculations." Journal of Chemical Physics 132(8):084501. doi:10.1063/1.3308499
Glezakou VA, and WA De Jong. 2011. "Cluster-Models for Uranyl(VI) Adsorption on alpha-Alumina." Journal of Physical Chemistry A 115(7):1257-1263.
Groenewold GS, MJ van Stipdonk, J Oomens, WA De Jong, and ME McIIwain. 2011. "The gas-phase bis-uranyl nitrate complex [(UO2)2(NO3)5]-: infrared spectrum and structure." International Journal of Mass Spectrometry 308(2-3):175-180. doi:10.1016/j.ijms.2011.06.002
Groenewold GS, MJ Van Stipdonk, J Oomens, WA De Jong, GL Gresham, and M Mcilwain. 2010. "Vibrational Spectra of Discrete UO?²? Halide Complexes in the Gas Phase." International Journal of Mass Spectrometry 297(1-3):67-75. doi:10.1016/j.ijms.2010.06.013
Groenewold GS, WA De Jong, J Oomens, and MJ Van Stipdonk. 2010. "Variable Denticity in Carboxylate Binding to the Uranyl Coordination Complexes." Journal of the American Society for Mass Spectrometry 21(5):719-727.
Kuta J, and AE Clark. 2010. "Trends in Aqueous Hydration Across the 4f Period Assessed by Reliable Computational Methods." Inorganic Chemistry 49(17):7808-7817. doi:10.1021/ic100623y
Kvamme B, MCF Wander, and AE Clark. 2009. "The Role of Basis Set Superposition Error in Water Addition Reactions to Ln(III) Cations." International Journal of Quantum Chemistry 109(11):2474-2481. doi:10.1002/qua.22139
Nichols PJ, N Govind, EJ Bylaska, and WA De Jong. 2009. "Gaussian Basis Set and Planewave Relativistic Spin-Orbit Methods in NWChem." Journal of Chemical Theory and Computation 5(3):491-499. doi:10.1021/ct8002892
Odoh SO, SM Walker, M Meier, J Stetefeld, and G Schreckenbach. 2011. "QM and QM/MM Studies of Uranyl Fluorides in the Gas and Aqueous Phases and in the Hydrophobic Cavities of Tetrabrachion." Inorganic Chemistry 50(7):3141-3152. doi:10.1021/ic2001706
Schoendorff GE, TL Windus, and WA De Jong. 2009. "Density Functional Studies on the Complexation and Spectroscopy of Uranyl Ligated with Acetonitrile and Acetone Derivatives." Journal of Physical Chemistry A 113(45):12525-12531.
Schoendorff GE, WA De Jong, MJ van Stipdonk, JK Gibson, D Rios, MS Gordon, and TL Windus. 2011. "On the Formation of "Hypercoordinated" Uranyl Complexes." Inorganic Chemistry 50(17):8490-8493. doi:10.1021/ic201080z
Schoendorff GE, WA De Jong, MS Gordon, and TL Windus. 2010. "Gas Phase Computational Studies on the Competition Between Nitrile and Water Ligands in Uranyl Complexes." Journal of Physical Chemistry A 114(33):8902-8912. doi:10.1021/jp103227x
Yang L, D Tunega, L Xu, N Govind, R Sun, R Taylor, H Lischka, WA De Jong, and WL Hase. 2013. "Comparison of Cluster, Slab, and Analytic Potential Models for the Dimethyl Methylphosphonate (DMMP)/TiO2 (110) Intermolecular Interaction ." Journal of Physical Chemistry C 117(34):17613-17622.