(gc3563)Molecular Computational Studies In Environmental Chemistry, Geochemistry, and Biogeochemistry
EMSL Project ID
3563
Abstract
Addressing the overwhelming environmental cleanup problems facing the Department of Energy?s nuclear production sites as well as other polluted sites in the nation is hampered by a lack of knowledge about many of the complex physical and chemical processes that can occur in the subsurface. High-performance computational molecular modeling of several areas of environmental chemistry, geochemistry, and biogeochemistry could significantly improve this situation by providing the development of a fundamental chemical understanding of many complex environmental and geochemical processes. Our proposed effort consists of a series of targeted molecular level simulations in key areas of environmental chemistry, geochemistry, and biogeochemistry. These simulations will be defined in five areas: chemistry of organochlorine compounds, aqueous speciation of metal ions and chelates, redox reactions at iron oxide surfaces, nanoparticle stability and oriented aggregation, and microbial-mineral interactions. By addressing these five different, but computationally related, areas it becomes possible to assemble a team of investigators with the necessary expertise in high performance computing and molecular simulation, as well as in environmental chemistry, geochemistry, and biogeochemistry to make continued and sustained progress in each area. Within each defined area, specific environmental chemisty, geochemistry and biogeochemistry issues are targeted. The summaries of each area are:Chemistry of organochlorine compounds: Characterize competing reaction mechanisms of the dechlorination of carbon tetrachloride and other organochlorine compounds in the subsurface environments
Aqueous speciation of metal ions and chelates: Understanding aqueous speciation under the unusual conditions, particularily highly basic conditions, where anions (silicate species) can show high solubilities and form complex polynuclear-metal complexes, or at high temperatures and pressures where a decreasing dielectric constant results in ever-increasing cation-anion associations.
Redox reactions at iron oxide surfaces: Studying the III/II valence interchange of iron (small polaron mobility) in iron oxides such as hematite (a?Fe2O3) and goethite (a?FeOOH)
Nanoparticle stability and oriented aggregation: identifying the factors governing the surface chemistry of iron oxide and oxyhydroxide nanoparticles in aqueous solution using large-scale molecular dynamics calculations.
Microbial surface mediated processes: the effects of lipopolysacchardies present on gram-negative bacteria.
By understanding on a fundamental basis these key issues, it is anticipated that the impacts of this research will be extendable to a wide range of environmental and geochemical. Taken in total such an effort truly represents a ?Grand Challenge? in molecular environmental chemistry, geochemistry, and biogeochemistry.
Project Details
Project type
Capability Research
Start Date
2003-10-01
End Date
2006-10-08
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Bickmore BR, KM Rosso, CJ Tadanier, EJ Bylaska, and D Doud. 2006. "Bond-valence methods for pKa prediction. II. Bond-valence, electrostatic, molecular geometry, and solvation effects ." Geochimica et Cosmochimica Acta 70(16):4057-4071.
Bogatko, S. A., E. J. Bylaska, Weare J.H. (2010). "First Principles Simulation of the Bonding, Vibrational, and Electronic Properties of the Hydration Shells of the High-Spin Fe3+ Ion in Aqueous Solutions." Journal of Physical Chemistry A 114(5): 2189-2200.
Bylaska EJ, DA Dixon, AR Felmy, E Apra, TL Windus, C Zhan, and PG Tratnyek. 2004. "The Energetics of the Hydrogenolysis, Dehydrohalogenation, and Hydrolysis of 4,4'-Dichloro-diphenyl-trichloroethane from Ab Initio Electronic Structure Theory." Journal of Physical Chemistry A 108(27):5883-5893.
Bylaska EJ, M Dupuis, and PG Tratnyek. 2005. "Ab Initio Electronic Structure Study of One-Electron Reduction Of Polychlorinated Ethylenes ." Journal of Physical Chemistry A 109(26):5905-5916.
Bylaska EJ, M Valiev, JR Rustad, and JH Weare. 2007. "Structure and Dynamics of the Hydration Shells of the Al3+ Ion ." Journal of Chemical Physics 126(10):Art.no.104505.
Casey WH, JR Rustad, D Banerjee, and G Furrer. 2005. "Large Molecules as Models for Small Particles in Aqueous Geochemistry Research." Journal of Nanoparticle Research 7(4-5):377-387. doi:10.1007/s11051-005-4718-8
Rosso KM, and M Dupuis. 2004. "Reorganization Energy Associated with Small Polaron Mobility in Iron Oxide." Journal of Chemical Physics 120(15):7050-7054.
Rosso KM, and M Dupuis. 2006. "Electron Transfer in Environmental Systems: A Frontier for Theoretical Chemistry ." Theoretical Chemistry Accounts 116(1-3):124-136. doi:10.1007/s00214-005-0016-x
Rustad JR. 2005. "Molecular Dynamics Simulation of the Titration of Polyoxocations in Aqueous Solution." Geochimica et Cosmochimica Acta 69(18):4397-4410. doi:10.1016/j.gca.2005.05.007
Rustad JR, and AR Felmy. 2005. "The Influence of Edge Sites on the Development of Surface Charge on Goethite Nanoparticles: A Molecular Dynamics Investigation." Geochimica et Cosmochimica Acta 69(6):1405-1411.
Rustad JR, and WH Casey. 2006. "A Molecular Dynamics Investigation of Hydrolytic Polymerization in a Metal-Hydroxide Gel." Journal of Physical Chemistry B 110(14):7107-7112. doi:10.1021/jp054379t
Rustad JR, and WH Casey. 2006. "A Molecular Dynamics Investigation of the Titration of a Trivalent Aqueous Ion." Theoretical Chemistry Accounts 115(2):136-144. doi:10.1007/s00214-005-0048-2
Rustad JR, JS Loring, and WH Casey. 2004. "Oxygen-exchange Pathways in Aluminum Polyoxocations." Geochimica et Cosmochimica Acta 68(14):3011-3017. doi:10.1016/j.gca.2003.12.021
Rustad JR, KM Rosso, and AR Felmy. 2004. "Molecular Dynamics Investigation of Ferrous-Ferric Electron Transfer in a Hydrolyzing Aqueous Solution: Calculation of the pH Dependence of the Diabatic Transfer Barrier and the Potential of Mean Force." Journal of Chemical Physics 120(16):7607-7615.
Stack AG, JR Rustad, and WH Casey. 2005. "Modeling Water Exchange on an Aluminum Polyoxocation." Journal of Physical Chemistry B 109(50):23771-23775. doi:10.1021/jp0530505
Stack AG, JR Rustad, J Deyoreo, T Land, and WH Casey. 2004. "The Growth Morphology of the {100} Surface of KDP (Archerite) on the Molecular Scale." Journal of Physical Chemistry B 108(47):18284-18290.
Swaddle TW, J Rosenquist, P Yu, EJ Bylaska, BL Phillips, and WH Casey. 2005. "Kinetic Evidence for Five-Coordination in AlOH(aq)2+ Ion." Science 308(5727):1450-1453.
Wang J, and JR Rustad. 2006. "A Simple Model for the Effect of Hydration on the Distribution of Ferrous Iron at Reduced Hematite (012) Surfaces." Geochimica et Cosmochimica Acta 70(21):5285-5292. doi:10.1016/j.gca.2006.08.022
Zhang H, and JF Banfield. 2004. "Aggregation, Coarsening, and Phase Transformation in ZnS Nanoparticles Studied by Molecular Dynamics Simulations." Nano Letters 4(4):713-718.
Zhang H, JR Rustad, and JF Banfield. 2007. "Interaction between Water Molecules and Zinc Sulfide Nanoparticles Studied by Temperature-Programmed Desorption and Molecular Dynamics Simulations." Journal of Physical Chemistry A 111(23):5008-5014