Computational Chemical Dynamics of Complex Systems
EMSL Project ID
47447
Abstract
The ultimate goal of this project is to develop and apply innovative user-friendly high-performance computing techniques and simulation methods for computational chemical dynamics of complex systems with special emphasis on a number of critical problems in environmental molecular science and chemical engineering facing the DOE and the nation. Recent advances in scientific computing allow for accurate (once infeasible) calculations of many interesting equilibrium and kinetic chemical properties. Nonetheless, applications to complex chemical systems, for example heterogeneous reactive processes or chemical reactions in the condensed phase, remain problematic due to the lack of a seamless integration of computational models that allow modern quantum electronic structure calculations to be combined with state-of-the-art methods for reactive dynamics and chemical thermodynamics. This project involves a collaboration of several faculty members and scientists at the University of Minnesota, the University of South Carolina, and the Pacific Northwest National Laboratory. The proposal is concerned with several fundamental areas of research including thermochemical kinetics and rate constants, photochemistry and spectroscopy, chemical and phase equilibria, and heterogeneous catalysis. These areas are important for solar energy, fuel-cell technology, environmental remediation, weather modeling, pollution modeling, and atmospheric chemistry. Special emphasis will be placed on the two EMSL themes: biological interactions and dynamics and the science of interfacial phenomena. Concerning the first theme, we will conduct a density functional theory (DFT) study of the photoenzymatic oxidation of water to molecular oxygen by the oxygen-evolving complex of photosystem II, which is a critical step in the bioutilization of solar energy. We plan a combined quantum-mechanics–molecular-mechanics study of biologically important enzymatic hydride transfer reactions. We will study explicit polarization effects in various biochemical systems, such as protein residues and hydrogen bond complexes using new semiempirical models and molecular mechanics force fields. We will also explore Feynman path integral methods in order to efficiently incorporate quantum effects such as tunneling and zero-point energy into the treatment of large molecules. In the field of interfacial phenomena, we propose a study on the rational design of novel electrodes for solid oxide fuel cells based on doped perovskite crystals. An additional project is a theoretical study of the oxidation mechanism of hydrogen at the nickel/yttria-stabilized–zirconia (Ni/YSZ) interface in the presence and absence of adsorbed sulfur, which can help to design more effective Ni/YSZ-based anodes for the electrochemical conversion of natural gas and coal gas. The proposal also involves studies of certain nucleation phenomena that are important in many environmental and technological processes. We are particularly interested in studying the formation of atmospheric sulfuric-acid–water–ammonia nanoparticles and the nucleation processes in silane-based plasmas. Another project is a computation of the potential energy surface of tetraoxygen (O4) followed by a study of the dynamics of O2–O2 collisions towards a better understanding of the stratospheric chemistry of oxygen. We will also study the dynamics of N2–N2 and N2–N dissociative collisions.
Project Details
Project type
Large-Scale EMSL Research
Start Date
2012-10-01
End Date
2013-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Co-Investigator(s)
Team Members
Related Publications
Aranifard S, SC Ammal, and A Heyden. 2014. "On the Importance of Metal–Oxide Interface Sites for the Water–Gas Shift Reaction Over Pt/CeO2 Catalysts." Journal of Catalysis 309:314-324. doi:10.1016/j.jcat.2013.10.012
Aranifard S, SC Ammal, and A Heyden. 2014. "On the Importance of the Associative Carboxyl Mechanism for the Water-Gas Shift Reaction at Pt/CeO2 Interface Sites." Journal of Physical Chemistry C. doi:10.1021/jp5000649
Duanmu K, and DG Truhlar. 2015. "Validation of Methods for Computational Catalyst Design: Geometries, Structures, and Energies of Neutral and Charged Silver Clusters." Journal of Physical Chemistry C 119(17):9617–9626. doi:10.1021/acs.jpcc.5b01545
Jalan A, IM Alecu, R Meana Paneda, J Aguilera-Iparraguirre, K Yang, SS Merchant, DG Truhlar, and WH Green. 2013. "New Pathways for Formation of Acids and Carbonyl Products in Low-Temperature Oxidation: The Korcek Decomposition of ??Ketohydroperoxides." Journal of the American Chemical Society 135(30):11100–11114. doi:10.1021/ja4034439
Jalan A, JW Allen, and WH Green. 2013. "Chemically Activated Formation of Organic Acids in Reactions of the Criegee Intermediate with Aldehydes and Ketones." Physical Chemistry Chemical Physics. PCCP. doi:10.1039/c3cp52598h
Meana Paneda R, YY Paukku, K Duanmu, P Norman, D Schwartzenberger, and DG Truhlar. 2015. "Atomic Oxygen Recombination at Surface Defects on Reconstructed (0001) ?-Quartz Exposed to Atomic and Molecular Oxygen." Journal of Physical Chemistry C 119(17):9287–9301. doi:10.1021/acs.jpcc.5b00120
Seal P, G Oyedepo, and DG Truhlar. 2013. "Kinetics of the Hydrogen Atom Abstraction Reactions from 1?Butanol by Hydroxyl Radical: Theory Matches Experiment and More." Journal of Physical Chemistry A 117(2):275-282. doi:10.1021/jp310910f
Suthirakun S, G Xiao, SC Ammal, F Chen, HC zur Loye, and A Heyden. 2013. "Rational Design of Mixed Ionic and Electronic Conducting Perovskite Oxides for Solid Oxide Fuel Cell Anode Materials: A Case Study for Doped SrTiO3." , Pacific Northwest National Laboratory, Richland, WA. doi:10.1016/j.jpowsour.2013.07.040 [Unpublished]
Suthirakun S, G Xiao, SC Ammal, F Chen, HC zur Loye, and A Heyden. 2014. "Rational Design of Mixed Ionic and Electronic Conducting Perovskite Oxides for Solid Oxide Fuel Cell Anode Materials: A case Study for Doped SrTiO3." Journal of Power Sources 245:875-885. doi:10.1016/j.jpowsour.2013.07.040
Suthirakun S, SC Ammal, AB Munoz-Garcia, G Xiao, F Chen, HC zur Loye, EA Carter, and A Heyden. 2014. "Theoretical Investigation of H2 Oxidation on the Sr2Fe1.5Mo0.5O6 (001) Perovskite Surface Under Anodic Solid Oxide Fuel Cell Conditions." Journal of the American Chemical Society 136(23):8374–8386. doi:10.1021/ja502629j
Xu X, W Zhang, M Tang, and DG Truhlar. 2015. "Do Practical Standard Coupled Cluster Calculations Agree Better than Kohn–Sham Calculations with Currently Available Functionals When Compared to the Best Available Experimental Data for Dissociation Energies of Bonds to 3d Transition Metals?" Journal of Chemical Theory and Computation 11(5):2036–2052. doi:10.1021/acs.jctc.5b00081
Yang K, A Jalan, WH Green, and DG Truhlar. 2013. "Which Ab Initio Wave Function Methods Are Adequate for Quantitative Calculations of the Energies of Biradicals? The Performance of Coupled-Cluster and Multi-Reference Methods Along a Single-Bond Dissociation Coordinate." Journal of Chemical Theory and Computation 9(1):418-431. doi:10.1021/ct3009528
Zheng J, P Seal, and DG Truhlar. 2013. "Role of Conformational Structures and Torsional Anharmonicity in Controlling Chemical Reaction Rates and Relative Yields: Butanal + HO2 Reactions." Chemical Science 4(1):200-212. doi:10.1039/c2sc21090h