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Reliable Relativistic Quantum Chemistry Calculations for Molecules with Heavy Elements


EMSL Project ID
9598

Abstract

We propose to perform ab initio electronic structure calculations based on wavefunction theory and density functional theory (DFT). The calculations will include a proper treatment of relativistic effects to investigate heavy element systems. Our computational studies will provide us with new understanding about the role of these effects in a broad range of chemical systems containing actinides, lanthanides, and heavy transition metals, all of which are critical to DOE missions including energy, environmental restoration, and Homeland Security. The specific molecular species to be studied will be selected in conjunction with other experimental and theoretical efforts at PNNL, other national laboratories, industry, and universities, with emphasis on DOE's environmental cleanup mission and on obtaining new scientific information about these novel molecular systems. This proposal is a renewal of our current, highly successful, EMSL Grand-Challenge project that will be ending this year.
A wide variety of relativistic and non-relativistic quantum chemical methods will be employed to explore actinide, lanthanide, heavy transition metal, and heavy main group element chemistry. Our goal is make use of state-of-the-art computational chemistry methods to give a firm theoretical basis to this area, to provide interpretations of complex experimental data, and to extend expensive experimental results into new areas of parameter space. Information that can be obtained for heavy element containing molecules includes, but is not limited to:
• Molecular structure and complex formation;
• Spectroscopic properties including electronic (e.g., UV-vis), vibrational (IR and Raman), and NMR;
• Complexation binding energies;
• Redox chemistry; and
• The role of solvation and other environmental effects
Our studies will contribute to the characterization of the interaction of the actinide, lanthanide and heavy transition metal ions with (organic) complexing agents that are present in nuclear processing waste tanks, and with anions that are present in natural aqueous systems (carbonates, silicates, etc.). The results will lead to a better understanding of 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 separation systems. The results of structural, spectroscopic, and energetics calculations will aid experimental researchers in their efforts to interpret complex experimental results and to provide a firm conceptual foundation for our understanding of these molecules. The proposed work will allow scientists to tackle the nature of excited states, a field that has been obscured by the difficulty of including multi-reference character and spin-orbit coupling effects, in heavy element compounds. 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 heavy transition metal elements, allowing limited experimental data to be extrapolated to many other regimes of interest.

Project Details

Project type
Capability Research
Start Date
2005-10-01
End Date
2008-10-05
Status
Closed

Team

Principal Investigator

Wibe De Jong
Institution
Lawrence Berkeley National Laboratory

Team Members

Sean Walker
Institution
University of Manitoba

Michael Kullman
Institution
Wichita State University

Niranjan Govind
Institution
Pacific Northwest National Laboratory

George Schoendorff
Institution
University of North Texas

Patrick Nichols
Institution
Pacific Northwest National Laboratory

Luiz De Macedo
Institution
São Paulo State University

Mark Rudolph
Institution
University at Buffalo, State University of New York

Changyong Qin
Institution
Washington State University

Aurora Clark
Institution
Washington State University

Brendan Mort
Institution
University at Buffalo, State University of New York

Vyacheslav Bryantsev
Institution
California Institute of Technology

Raluca Craciun
Institution
University of Alabama

Alexei Yakovlev
Institution
Scientific Computing & Modeling N.V.

Vassiliki-Alexandra Glezakou
Institution
Pacific Northwest National Laboratory

Hasan Sayin
Institution
Auburn University

Hyun Joo
Institution
University of the Pacific

Christoph Jacob
Institution
Vrije Universiteit Amsterdam

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

Mariusz Sterzel
Institution
University at Buffalo, State University of New York

Angela Wilson
Institution
Michigan State University

Theresa Windus
Institution
Iowa State University

Michael Perkins
Institution
Pacific Northwest National Laboratory

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

Walter Ermler
Institution
Self (Ermler)

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

Enrique Batista
Institution
Los Alamos National Laboratory

Michael Mckee
Institution
Auburn University

William Goddard
Institution
California Institute of Technology

Jason Sonnenberg
Institution
The Ohio State University

Related Publications

Bryantsev V, WA De Jong, KC Cossel, MS Diallo, WA Goddard III, GS Groenewold, W Chien, and MJ Van Stipdonk. 2008. "Two-Electron Three-Centered Bond in Side-On (η2) Uranyl(V) Superoxo Complexes." Journal of Physical Chemistry A 112(26):5777-5780. doi:10.1021/jp804202q
Clark, A. E. "Density Functional and Basis Set Dependence of Hydrated Ln(III) Properties" Journal of Chemical Theory and Computation, 4:708-718. DOI: 10.1021/ct700317p
De Macedo LGM, and WA De Jong. 2008. "Fully Relativistic Calculations on the Potential Energy Surfaces of the Lowest 23 States of Molecular Chlorine." Journal of Chemical Physics 128(4):Art. No. 041101. doi:10.1063/1.2827457
DInescu, A.; Clark, A. E. "Thermodynamic and Structural Features of Aqueous Ce(III)" Journal of Physical Chemistry A 112:11198–11206. DOI: 10.1021/jp8076408
Fleig T, HJ Jensen, J Olsen, and L Visscher. 2006. "The generalized active space concept for the relativistic treatment of electron correlation. III. Large-scale configuration interaction and multiconfiguration self-consistent-field four-component methods with application to UO₂. ." Journal of Chemical Physics 124(104106):1-11. doi:10.1063/1.2176609
Groenewold GS, AK Gianotto, KC Cossel, MJ Van Stipdonk, DT Moore, N Polfer, J Oomens, WA De Jong, and L Visscher. 2006. "Vibrational Spectroscopy of Mass-Selected [UO₂(ligand)n]²⁺ Complexes in the Gas Phase: Comparison with Theory." Journal of the American Chemical Society 128(14):4802-4813. doi:10.1021/ja058106n
Groenewold GS, AK Gianotto, KC Cossel, MJ Van Stipdonk, J Oomens, N Polfer, D Moore, WA De Jong, and ME McIIwain. 2007. "Mid-Infrared Vibrational Spectra of Discrete Acetone-Ligated Cerium Hydroxide Cations." Physical Chemistry Chemical Physics. PCCP 9(5):596-606.
Groenewold GS, AK Gianotto, ME McIIwain, MJ Van Stipdonk, M Kullman, DT Moore, N Polfer, J Oomens, IA Infante, L Visscher, B Siboulet, and WA De Jong. 2008. "Infared Spectroscopy of Discrete Uranyl Anion Complexes." Journal of Physical Chemistry A 112(3):508-521. doi:10.1021/jp077309q
Groenewold GS, J Oomens, WA De Jong, GL Gresham, ME McIIwain, and MJ Van Stipdonk. 2008. "Vibrational Spectroscopy of Anionic Nitrate Complexes of UO₂2+ and Eu³+ Isolated in the Gas Phase." Physical Chemistry Chemical Physics. PCCP 10(8):1192-1202. doi:10.1039/b715337f
Groenewold GS, MJ Van Stipdonk, WA De Jong, J Oomens, GL Gresham, ME McIIwain, D Gao, B Siboulet, L Visscher, M Kullman, and N Polfer. 2008. "Infrared Spectroscopy of Dioxouranium (V) Complexes with Solvent Molecules: Effect of Reduction." Chemphyschem 9(9):1278-1285. doi:10.1002/cphc.200800034
Gutowski KE, and DA Dixon. 2006. "Predicting the Energy of the Water Exchange Reaction and Free Energy of Solvation for the Uranyl Ion in Aqueous Solution." Journal of Physical Chemistry A 110(28):8840-8856.
Gutowski KE, VA Cocalia, ST Griffin, NJ Bridges, DA Dixon, and RD Rogers. 2007. "Interactions of 1-Methylimidazole with UO₂(CH₃CO₂)₂ and UO₂(NO₃)₂: Structural, Spectroscopic, and Theoretical Evidence for Imidazole Binding to the Uranyl Ion." Journal of the American Chemical Society 129(3):526-536.
Infante IA, and L Visscher. 2003. "A QM/MM Study of Aqueous Solvation of the Uranyl Fluoride [UO₂F₄₂₋] Complex." Journal of Computational Chemistry 25(3):386-392.
Infante IA, A Severo, P Gomes, and L Visscher. 2006. "On the performance of the intermediate Hamiltonian Fock-space coupled-cluster method on linear triatomic molecules: The electronic spectra of NpO₂+, NpO₂ ²+, and PuO₂ ²+. ." Journal of Chemical Physics 125(7):074301 (1-9). doi:10.1063/1.2244564
Infante IA, B van Stralen, and L Visscher. 2006. "A QM/MM Study on the Aqueous Solvation of the Tetrahydroxouranylate [UO₂(OH)₄]²⁻ Complex ion." Journal of Computational Chemistry 27(11):1156-1162. doi:10.1002/jcc.20434
Jackson VE, RN Craciun, DA Dixon, KA Peterson, and WA De Jong. 2008. "Prediction of the Vibrational Frequencies of UO₂²+ at the CCSD(T) Level." Journal of Physical Chemistry A 112(17):4095-4099.
Jacob C, J Neugebauer, L Jensen, and L Visscher. 2006. "Comparison of Frozen-density Embedding and Discrete Reaction Field Solvent Models for Molecular Properties." Physical Chemistry Chemical Physics. PCCP 8(20):2349-2359. doi:10.1039/b601997h
Leavitt CM, VS Bryantsev, WA De Jong, MS Diallo, WA Goddard III, GS Groenewold, and MJ Van Stipdonk. 2009. "Addition of H2O and O-2 to Acetone and Dimethylsulfoxide Ligated Uranyl(V) Dioxocations." Journal of Physical Chemistry A 113(11):2350-2358. doi:10.1021/jp807651c
Nichols P, EJ Bylaska, GK Schenter, and WA De Jong. 2008. "Equatorial and Apical Solvent Shells of the UO₂²⁺ Ion." Journal of Chemical Physics 128(12):124507.
Sterzel M, and J Autschbach. 2006. "Toward an Accurate Determination of 195Pt Chemical Shifts by Density Functional Computations: The Importance of Unspecific Solvent Effects and the Dependence of Pt Magnetic Shielding Constants on Structural Parameters." Inorganic Chemistry 45(8):3316-3324. doi:10.1021/ic052143y
Wang X, L Andrews, and J Li. 2006. "Experimental and Theoretical Investigations of IR Spectra and Electronic Structures of the U(OH)₂, UO₂(OH), and UO₂(OH)₂ Molecules." Inorganic Chemistry 45(10):4157-4166.