(gc3565)Reliable Electronic Structure Prediction of Molecular Properties
EMSL Project ID
3565
Abstract
The area of environmental chemical science is dominated by issues of scaling in space and time. The goal of environmental science is to understand the current state of the environment based on our knowledge of the past and to use this information to be able to predict the future state. For example, given current practices for manufacturing, what will be their long-term environmental impact? Given potential environmental remediation strategies, what will these lead to? One does not want to use a remediation strategy that will have unforeseen consequences and introduce new environmental issues. No one wants to repeat the mistakes of the past, for example, the widespread release of chlorofluorocarbons (CFC?s) into the atmosphere. Although, we are interested in the results at large spatial and temporal scales, detailed insight into behavior at the molecular scale is key to understanding (1) how humans have impacted the environment, (2) how to remediate anthropogenic impacts on the environment, and (3) how to minimize future anthropogenic impacts. Of particular interest are reliable, accurate values for thermodynamic and kinetic properties of molecules that can be used in molecular design, in process design and in remediation models. Computational chemistry is a key technology for addressing the complex environmental cleanup problems facing the Department of Energy?s nuclear production sites, as well as the problems associated with other polluted sites in the United States and the prevention of further pollution. High accuracy from a simulation is important. A factor of 2 to 4 in catalyst efficiency may determine whether a chemical process is economically feasible or not and a factor of 4 in a rate constant at room temperature (25oC) corresponds to a change in the activation energy on the order of just less than 1 kcal/mol. Given a 50:50 starting mixture of two components, a change in the free energy, G, of less than 1.5 kcal/mol leads to a change in the equilibrium constant by a factor of 10, leading to a 90:10 mixture at 25oC. The requirement for such accuracy means that we must be able to predict thermodynamic quantities such as bond dissociation energies (De or D00) and heats of formation (Hf) to better than 1 kcal/mol and activation energies to within a few tenths of a kcal/mol ? a daunting computational task. Our goal is to develop and test the procedures needed to provide accurate predictions of such molecular properties. We will then apply such tools to the prediction of a variety of molecular properties and systems including: transition metal compounds, host/guest complexes for the design of separation systems, combustion related compounds including the propargyl potential energy surface, anionic states of solvated nucleic acid bases and amino acids related to low dose biochemistry, development of flexible, polarizable interaction potentials for water-water and ion-water interactions, high cccuracy thermochemistry for molecules including fluorinated compounds and biological molecules relevant to phosphorylation processes, novel gas phase anion including clusters, inorganic complexes, and the effects of solvation, and theoretical studies of the mechanisms of hydrolytic reactions.
Project Details
Project type
Capability Research
Start Date
2006-02-03
End Date
2006-10-25
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Density functional theory calculations of redox properties of iron–sulphur protein analogues
Niu S, and T Ichiye. 2011. "Density Functional Theory Calculations of Redox Properties of Iron–Sulphur Protein Analogues." Molecular Simulation 37(7):572-590. doi:10.1080/08927022.2011.582111
Insight into Environmental Effects on Bonding and Redox Properties of [4Fe-4S] Clusters in Proteins
Niu S, and T Ichiye. 2009. "Insight into Environmental Effects on Bonding and Redox Properties of [4Fe-4S] Clusters in Proteins." Journal of the American Chemical Society 131(16):5724-5725. doi:10.1021/ja900406j
Probing Ligand Effects on the Redox Energies of [4Fe−4S] Clusters Using Broken-Symmetry Density Functional Theory
Niu S, and T Ichiye. 2009. "Probing Ligand Effects on the Redox Energies of [4Fe-4S] Clusters Using Broken-Symmetry Density Functional Theory." Journal of Physical Chemistry A 113(19):5671–5676. doi:10.1021/jp809446q
Sn122-: Stannaspherene
Cui L, X Huang, L Wang, DY Zubarev, AI Boldyrev, J Li, and LS Wang. 2006. "Sn₁₂²⁻: Stannaspherene." Journal of the American Chemical Society 128(26):8390-8391. doi:10.1021/ja062052f
Interactions of 1-Methylimidazole with UO2(CH3CO2)2 and UO2(NO3)2: Structural, Spectroscopic, and Theoretical Evidence for Imidazole Binding to the Uranyl Ion
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. doi:10.1021/ja064592i
The Flexible, Polarizable, Thole-Type Interaction Potential for Water (TTM2-F) Revisited
Fanourgakis GS, and SS Xantheas. 2006. "The flexible, polarizable, thole-type interaction potential for water (TTM2-F) Revisited." Journal of Physical Chemistry A 110(11):4100-4106. doi:10.1021/jp056477k
Theoretical Prediction of the Heats of Formation of C2H5O• Radicals Derived from Ethanol and of the Kinetics of β-C−C Scission in the Ethoxy Radical
Matus MH, MT Nguyen, and DA Dixon. 2007. "Theoretical Prediction of the Heats of Formation of C₂H₅O● Radicals Derived from Ethanol and of the Kinetics of β-C-C Scission in the Ethoxy Radical." Journal of Physical Chemistry A 111(1):113-126. doi:10.1021/jp064086f
Gas-phase acidities of aspartic acid, glutamic acid, and their amino acid amides
Li Z, MH Matus, HA Velazquez, DA Dixon, and CJ Cassady. 2007. "Gas-phase Acidities of Aspartic Acid, Glutamic Acid, and their Amino Acid Amides." International Journal of Mass Spectrometry 265(2-3):213-223. doi:10.1016/j.ijms.2007.02.009
Accurate Thermochemical Properties for Energetic Materials Applications. I. Heats of Formation of Nitrogen-Containing Heterocycles and Energetic Precursor Molecules from Electronic Structure Theory
Gutowski KE, RD Rogers, and DA Dixon. 2006. "Accurate Thermochemical Properties for Energetic Materials Applications. I. Heats of Formation of Nitrogen-Containing Heterocycles and Energetic Precursor Molecules from Electronic Structure Theory." Journal of Physical Chemistry A 110(42):11890-11897. doi:10.1021/jp0643698
Thermochemical Properties of HxNO Molecules and Ions from ab Initio Electronic Structure Theory
Dixon DA, JS Francisco, and Y Alexeev. 2006. "Thermochemical Properties of HxNO Molecules and Ions from ab Initio Electronic Structure Theory." Journal of Physical Chemistry A 110(1):185-191. doi:10.1021/jp054642q
The Heats of Formation of Diazene, Hydrazine, N2H3+, N2H5+, N2H, and N2H3 and the Methyl Derivatives CH3NNH, CH3NNCH3, and CH3HNNHCH3
Matus MH, AJ Arduengo, III, and DA Dixon. 2006. "The Heats of Formation of Diazene, Hydrazine, N₂H₃ ⁺, N₂H₅ +, N₂H, and N₂H₃ and the Methyl Derivatives CH₃NNH, CH₃NNCH₃, and CH₃HNNHCH₃." Journal of Physical Chemistry A 110(33):10116-10121. doi:10.1021/jp061854u
Bound anionic states of adenine
Haranczyk M, MS Gutowski, X Li, and KH Bowen. 2007. "Bound anionic states of adenine." Proceedings of the National Academy of Sciences of the United States of America 104(12):4804-4807. doi:10.1073/pnas.0609982104