Skip to main content

(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

Team

Principal Investigator

Wibe De Jong
Institution
Lawrence Berkeley National Laboratory

Team Members

Alexei Yakovlev
Institution
Scientific Computing & Modeling N.V.

Shenggang Li
Institution
University of Alabama

Keith Gutowski
Institution
University of Notre Dame

Jochen Autschbach
Institution
University at Buffalo, State University of New York

Tianxiao Yang
Institution
The Ohio State University

Boris LeGuennic
Institution
University at Buffalo, State University of New York

Angela Wilson
Institution
Michigan State University

Timothy Firman
Institution
Pacific Northwest National Laboratory

Erick Palmer
Institution
The Ohio State University

Ivan Infante
Institution
Vrije Universiteit Amsterdam

Chang-guo Zhan
Institution
University of Kentucky

Stan Van Gisbergen
Institution
Vrije Universiteit Amsterdam

Benjamin Hay
Institution
Oak Ridge National Laboratory

David Dixon
Institution
University of Alabama

Maria Marino
Institution
University of Texas at San Antonio

Walter Ermler
Institution
Self (Ermler)

Robert Harrison
Institution
University of Tennessee

Kimihiko Hirao
Institution
The University of Tokyo

Lucas Visscher
Institution
Vrije Universiteit Amsterdam

Zhiyong Zhang
Institution
Stanford University

Bruce Bursten
Institution
The Ohio State University

Kenneth Dyall
Institution
Schrodinger, Inc.

Jun Li
Institution
Tsinghua University

Spiridoula Matsika
Institution
Temple University

Paul Bagus
Institution
University of North Texas

Jason Sonnenberg
Institution
The Ohio State University

Related Publications

Ab initio study of AmCl¿: f–f spectroscopy and chemical binding
Andrews L, B Liang, J Li, and BE Bursten. 2004. "Noble Gas-Uranium Coordination and Intersystem Crossing for the CUO(Ne)x(Ng)n (Ng = Ar, Kr, Xe) Complexes in Solid Neon." New Journal of Chemistry 28(2):289-294.
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
Bagus P, and ES Ilton. 2006. "Effects of Covalency on the p-Shell Photoemission of Transition Metals: MnO." Physical Review. B, Condensed Matter 73(15):155110.
Bagus PS, R Broer, and ES Ilton. 2004. "A New Near Degeneracy Effect for Photoemission in Transition Metals.." Chemical Physics Letters 394(1-3):150-154.
Hay BP, TK Firman, and BA Moyer. 2005. "Structural Design Criteria for Anion Hosts: Strategies for Achieving Anion Shape Recognition through the Complementary Placement of Urea Donor Groups." Journal of the American Chemical Society 127(6):1810-1819.
Ilton ES, and P Bagus. 2005. "Many-body Effects in the 4f X-ray Photoelectron Spectroscopy of the U5+ and U4+ Free Ions." Physical Review. B, Condensed Matter 71(19):195121.
Ilton ES, WA De Jong, and P Bagus. 2003. "Intra Atomic Many-Body Effects in P-shell Photoelectron Spectra of Cr3+ Ions." Physical Review. B, Condensed Matter and Materials Physics 68(12):125106.
NMR properties of platinum–thallium bonded complexes: analysis of relativistic density functional theory results
Relativistic quadruple-zeta and revised triple-zeta and double-zeta basis sets for the 4p, 5p, and 6p elements
The invisible 13C chemical shift of the central carbon atom in [(Ph3PAu)6C]2+. A theoretical investigation
TK Firman, BP Hay, and Bryantsev V. 2005. "Conformational Analysis and Rotational Barriers of Alkyl- and Phenyl-Substituted Urea Derivatives ." Journal of Physical Chemistry A 109(5):832-842.
Wang X, L Andrews, J Li, and BE Bursten. 2004. "Significant Interactions between Uranium and Noble-Gas Atoms: Coordination of the UO2+ Cation by Ne, Ar, Kr, and Xe Atoms." Angewandte Chemie International Edition 43(19):2554-2557.