Reliable Electronic Structure Prediction of Molecular Properties
EMSL Project ID
20901
Abstract
The field of environmental 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 make forward predictions. 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? The use of remediation strategies should be based on a solid understanding of their long-term impact on the environment in order to avoid unforeseen consequences such as the past widespread release of chlorofluorocarbons (CFCs) into the atmosphere. Although the interest is clearly in the results at large spatial and temporal scales, detailed insight into behavior at the molecular scale is key to the understanding of (i) how humans have impacted the environment, (ii) how to remediate anthropogenic impacts on the environment, and (iii) how to minimize future anthropogenic impacts. Of particular interest are reliable, accurate values for thermodynamic and kinetic properties of molecular systems that can be used in molecular design, in process design, for example, studies of combustion, and in remediation models. Computational chemistry is a key technology for addressing the complex environmental cleanup problems facing the Department of Energys nuclear production sites, as well as the problems associated with other polluted sites in the United States and the prevention of further pollution. The issue of accuracy as the result of a simulation is very important. For instance, 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, ΔG, 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 (ΔHf) of small molecules and molecular clusters 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 then apply such tools to the prediction of a variety of molecular properties and systems including: transition metal compounds, combustion related compounds including the propargyl potential energy surface and alkane and alkoxy radical bond energies, main group chemistry including highly reactive compounds with high oxidation states and mono-, di- and tri-phosphate compounds, host/guest complexes for the design of separation systems such as clathrate hydrates and metal ion receptors, and iron-sulfur proteins.
Project Details
Project type
Capability Research
Start Date
2006-10-01
End Date
2009-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Is Electronegativity a Useful Descriptor for the Pseudo-Alkali Metal NH4?
Whiteside, A., Xantheas, S. S. and Gutowski, M. (2011), Is Electronegativity a Useful Descriptor for the Pseudo-Alkali Metal NH4?. Chemistry - A European Journal, 17: 13197?13205. doi: 10.1002/chem.201101949
Photoelectron spectrum of valence anions of uracil and first-principles calculations of excess electron binding energies
Bachorz RA, WM Klopper, MS Gutowski, X Li, and KH Bowen. 2008. "Photoelectron Spectrum of Valence Anions of Uracil and First-principles Calculations of Excess Electron Binding Energies." Journal of Chemical Physics 129:054309. doi:10.1063/1.2965128
Energetics and Dynamics of Electron Transfer and Proton Transfer in Dissociation of MetalIII(salen)−Peptide Complexes in the Gas Phase
Laskin J, Z Yang, and IK Chu. 2008. "Energetics and Dynamics of Electron Transfer and Proton Transfer in Dissociation of Metal III (salen)-Peptide Complexes in the Gas Phase." Journal of the American Chemical Society 130(10):3218-3230. doi:10.1021/ja077690s
On the Determination of Monomer Dissociation Energies of Small Water Clusters from Photoionization Experiments
Kathmann SM, GK Schenter, and SS Xantheas. 2008. "On the Determination of Monomer Dissociation Energies of Small Water Clusters from Photoionization Experiments." Journal of Physical Chemistry A 112(9):1851-1853. doi:10.1021/jp710624r
A unique coplanar multi-center bonding network in doubly acetylide-bridged binuclear zirconocene complexes: A density functional theory study
Niu S, A Derecskei-Kovacs, and MB Hall. 2007. "A Unique Coplanar Multi-center Bonding Network in Doubly Acetylide-bridged Binuclear Zirconocene Complexes: A Density Functional Theory Study." Journal of Organometallic Chemistry 692(21):4760-4767. doi:10.1016/j.jorganchem.2007.07.019
Cleavage of [4Fe—4S]-Type Clusters: Breaking the Symmetry
Niu S, and T Ichiye. 2009. "Cleavage of [4Fes4S]-Type Clusters: Breaking the Symmetry." Journal of Physical Chemistry A 113(19):5710-5717. doi:10.1021/jp900402y
The Effect of the Secondary Structure on Dissociation of Peptide Radical Cations: Fragmentation of Angiotensin III and Its Analogues
Yang Z, C Lam, IK Chu, and J Laskin. 2008. "The Effect of the Secondary Structure on Dissociation of Peptide Radical Cations: Fragmentation of Angiotensin III and Its Analogues." Journal of Physical Chemistry B 112(39):12468-12478. doi:10.1021/jp805226x
Observation of terahertz vibrations in Pyrococcus furiosus rubredoxin via impulsive coherent vibrational spectroscopy and nuclear resonance vibrational spectroscopy – interpretation by molecular mechanics
Tan ML, AR Bizzarri, Y Xiao, S Cannistraro, T Ichiye, C Manzoni, G Cerullo, MW Adams, FE Jenney, and SP Cramer. 2007. "Observation of Terahertz Vibrations in Pyrococcus Furiosus Rubredoxin Via Impulsive Coherent Vibrational Spectroscopy and Nuclear Resonance Vibrational Spectroscopy – Interpretation by Molecular Mechanics." Journal of Inorganic Biochemistry 101(3):375-384. doi:10.1016/j.jinorgbio.2006.09.031
Dynamics of Rhodobacter capsulatus [2Fe-2S] Ferredoxin VI and Aquifex aeolicus Ferredoxin 5 via Nuclear Resonance Vibrational Spectroscopy (NRVS) and Resonance Raman Spectroscopy
Xiao Y, ML Tan, T Ichiye, H Wang, Y Guo, MC Smith, J Meyer, W Sturhahn, EE Alp, J Zhao, Y Yoda, and SP Cramer. 2008. "Dynamics of Rhodobacter Capsulatus [2FE-2S] Ferredoxin VI and Aquifex Aeolicus Ferredoxin 5 Via Nuclear Resonance Vibrational Spectroscopy (NRVS) and Resonance Raman Spectroscopy." Biochemistry 47(25):6612-6627. doi:10.1021/bi701433m
Visualization of Molecular Orbitals and the Related Electron Densities
Haranczyk M, and MS Gutowski. 2008. "Visualization of Molecular Orbitals and the Related Electron Densities." Journal of Chemical Theory and Computation 4(5):689-693. doi:10.1021/ct800043a
Adiabatically Bound Valence Anions of Guanine
Haranczyk M, MS Gutowski, X Li, and KH Bowen. 2007. "Adiabatically Bound Valence Anions of Guanine." Journal of Physical Chemistry B 111(51):14073-14076. doi:10.1021/jp077439z
Intermolecular proton transfer induced by excess electron attachment to adenine(formic acid)n (n=2, 3) hydrogen-bonded complexes
Mazurkiewicz K, M Haranczyk, P Storoniak, MS Gutowski, J Rak, D Radisic, S Eustis, D Wang, and KH Bowen. 2007. "Intermolecular proton transfer induced by excess electron attachment to adenine(formic acid)n (n = 2, 3) hydrogen-bonded complexes." Chemical Physics 342(1-3):215-222. doi:10.1016/j.chemphys.2007.10.005
Comparison of some representative density functional theory and wave function theory methods for the studies of amino acids
Yu W, L Liang, Z Lin, S Ling, M Haranczyk, and MS Gutowski. 2009. "Comparison of Some Representative Density Functional Theory and Wave Function Theory Methods for the Studies of Amino Acids." Journal of Computational Chemistry 30(4):589-6006. doi:10.1002/jcc.21091
Observation of earlier two-to-three dimensional structural transition in gold cluster anions by isoelectronic substitution: MAun− (n=8–11; M=Ag,Cu)
Lei-Ming Wang,Rhitankar Pal, Wei Huang, Xiao Cheng Zeng, and
Lai-Sheng Wang. 2010. "Observation of earlier two-to-three dimensional structural transition
in gold cluster anions by isoelectronic substitution: MAun ? (n=8–11; M=Ag,Cu)." THE JOURNAL OF CHEMICAL PHYSICS 132, 114306. doi:10.1063/1.3356046
Lai-Sheng Wang. 2010. "Observation of earlier two-to-three dimensional structural transition
in gold cluster anions by isoelectronic substitution: MAun ? (n=8–11; M=Ag,Cu)." THE JOURNAL OF CHEMICAL PHYSICS 132, 114306. doi:10.1063/1.3356046
Isomer identification and resolution in small gold clusters
Wei Huang, Rhitankar Pal, Lei-Ming Wang, Xiao Cheng Zeng, and
Lai-Sheng Wang. 2010. " Isomer identification and resolution in small gold clusters." THE JOURNAL OF CHEMICAL PHYSICS 132, 054305. doi:10.1063/1.3299292
Lai-Sheng Wang. 2010. " Isomer identification and resolution in small gold clusters." THE JOURNAL OF CHEMICAL PHYSICS 132, 054305. doi:10.1063/1.3299292
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
Identifying the most stable networks in polyhedral water clusters
Kirov MV, GS Fanourgakis, and SS Xantheas. 2008. "Identifying the Most Stable Networks in Polyhedral Water Clusters." Chemical Physics Letters 461(4-6):180-188. doi:10.1016/j.cplett.2008.04.079