(gc3-2002)Reliable Electronic Structure Calculations for Heavy Element Chemistry: Molecules Containing Actinides, Lanthanides, and Transition Metals
EMSL Project ID
2385
Abstract
We propose to perform ab initio electronic structure calculations based on molecular orbital theory and density functional theory with the proper treatment of relativistic effects to study complexes of heavy elements in order to assist in understanding and predicting the chemistry of the actinides, lanthanides, and heavy transition metals - molecules critical to DOE missions including environmental management. The specific molecular species to be studied will be selected in conjunction with experimental and theoretical efforts at PNNL and elsewhere with emphasis on the environmental restoration needs of the DOE. A wide variety of relativistic and non-relativistic quantum chemical methods will be used to assist in the understanding and prediction of actinide, lanthanide, and transition metal chemistry with the goal of giving a firm theoretical basis to this area, and to extending expensive experimental results into new areas of parameter space. Information that can be provided for actinide containing molecules includes, but is not limited to: ? Molecular structure and complex formation ? Spectroscopic properties including electronic, vibrational and NMR ? Complexation binding energies, redox chemistry, and solvation effects and energies. This data will contribute to the characterization of the interaction of the actinide, lanthanide and heavy transition metal ions with organic complexing agents present in nuclear processing waste tanks and with anion ligands present in natural aqueous systems (e.g., carbonates) in order to better understand their fate and transport in the environment, as well as interactions with new materials such as phosphates and amides for the design of innovative in situ remediation technologies and novel separation systems. In addition, the proposed work will allow scientists to tackle the complexity of excited states in heavy element compounds especially those comprised of actinide, lanthanide, and heavy transition metal atoms. The theoretical and computational results obtained from our calculations will be an invaluable supplement to current, very expensive experimental studies of the actinides, lanthanides, and radioactive heavy transition metal elements, allowing limited experimental data to be extrapolated to many other regimes of interest. The software that will be used consists of the NWChem, Amsterdam Density Functional (ADF) and Columbus software suites for approximate relativistic methodologies, and the MOLFDIR and DIRAC software suites for fully relativistic benchmark calculations. The proposal?s objectives will be attained through a multi-site collaboration from PNNL, Ohio State University, Stevens Institute of Technology, Eloret, the Free University of Amsterdam (Netherlands), the University of Paul Sabatier (Toulouse, France), and the University of Tokyo (Japan). The collaboration includes leading researchers in the areas of high-performance computational chemistry and relativistic theoretical chemistry.
Project Details
Project type
Capability Research
Start Date
2001-10-01
End Date
2004-10-05
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Scalar Relativistic Computations and Localized Orbital Analyses of Nuclear Hyperfine Coupling and Paramagnetic NMR Chemical Shifts
Aquino FW, B Pritchard, and J Autschbach. 2012. "Scalar Relativistic Computations and Localized Orbital Analyses of Nuclear Hyperfine Coupling and Paramagnetic NMR Chemical Shifts." Journal of Chemical Theory and Computation 8(2):598-609. doi:10.1021/ct2008507