Computational Chemical Dynamics of Complex Systems
EMSL Project ID
34900
Abstract
The objective of this project is to develop and apply innovative high-performance computing techniques and simulation methods in order to address computationally challenging problems in chemical dynamics, with special emphasis on the critical problems in environmental science and chemical engineering facing the DOE and the nation. 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. These computationally intensive studies will be carried out with new high-throughput integrated software that we have been developing. The development of compatible, portable, scalable, and user-friendly computational tools that combine electronic structure packages with dynamics codes and efficient sampling algorithms will be continued as part of this project. The proposal features four EMSL themes: atmospheric aerosol chemistry, biological interactions and dynamics, geochemistry and subsurface science, and science of interfacial phenomena. In the field of atmospheric aerosol chemistry, we propose a study of nucleation phenomena which play a pivotal role in many atmospheric and technological processes. We propose to develop paradigm-shifting, scalable computational approaches for modeling the nucleation, structure, and properties of nanodroplets. Another aspect of our research is the development of efficient and robust methods for analytical representations of multidimensional potential energy surfaces for photochemical reactions including those of environmental and energetic importance. In the field of biological interactions and dynamics, we will study explicit polarization effects in various molecules and biochemical systems, such as protein residues and hydrogen bond complexes using re-parametrized semiempirical models and molecular mechanics force fields. We will also explore Feynman path integral methods in order to incorporate quantum effects such as tunneling and zero-point energy into the treatment of large molecules. In the field of geochemistry and subsurface science, we propose large-scale Monte Carlo simulations of silica melts. Silica plays a significant role in the chemistry and mineralogy of the Earth's crust and mantle. In the field of interfacial phenomena, we propose to provide molecular-level insights on retention mechanisms in reversed-phase liquid chromatography. These mechanisms are not well understood and there remain many open questions on bonded-phase conformation, solvent penetration, solvophobic versus lipophilic interactions, and partition versus adsorption. We are interested in studying interfacial phenomena related to heterogeneous catalysis, especially, involving transition-metal compounds and zeolite frameworks. In particular, we plan to study the electrochemistry of water oxidation by binuclear copper and ruthenium catalysts. The water oxidation process is a difficult component of the challenge to efficiently convert solar radiation into a chemical fuel. Another area of interest is a study of nano-gold clusters in order to relate their optical and structural properties to their enhanced catalytic activity in CO oxidation. We will also develop new potential energy functions for the study of adsorption isotherms of hydrocarbons in zeolites and we will interface the new potentials with a Monte Carlo Gibbs ensemble algorithm to calculate the adsorption isotherms. In addition, substantial efforts will be put in the modeling of ion solvation and ion transport through biological membranes, geological minerals, or in electrolytes.
Project Details
Project type
Capability Research
Start Date
2009-10-14
End Date
2012-09-30
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Ammal SC, and A Heyden. 2010. "Modeling the Noble Metal/TiO2 (110) Interface with Hybrid DFT Functionals: A Periodic Electrostatic Embedded Cluster Model Study." Journal of Chemical Physics 133(16):164703 to 164703-15. doi:10.1063/1.3497037
Ammal SC, and A Heyden. 2011. "Nature of Ptn/TiO2(110) Interface under Water-Gas Shift Reaction Conditions: A Constrained ab Initio Thermodynamics Study." Journal of Physical Chemistry C 115(39):19246-19259. doi:10.1021/jp2058723
Averkiev BB, Y Zhao, and DG Truhlar. 2010. "Binding Energy of d¹º Transition Metals to Alkenes By Wave Function Theory and Density Functional Theory." Journal of Molecular Catalysis. A, Chemical. 324(1-2):80-88. doi:10.1016/j.molcata.2010.03.016
Chuev GN, M Valiev, and MV Fedotova. 2012. "Integral Equation Theory of Molecular Solvation Coupled with Quantum Mechanical/Molecular Mechanics Method in NWChem Package." Journal of Chemical Theory and Computation 8(4):1246-1254. doi:10.1021/ct2009297
Marenich A, W Ding, CJ Cramer, and DG Truhlar. 2012. "Resolution of a Challenge for Solvation Modeling: Calculation of Dicarboxylic Acid Dissociation Constants Using Mixed Discrete?Continuum Solvation Models." The Journal of Physical Chemistry Letters 3(11):1437-1442. doi:10.1021/jz300416r
Papajak E, and DG Truhlar. 2011. "Convergent Partially Augmented Basis Sets for Post-Hartree-Fock Calculations of Molecular Properties and Reaction Barrier Heights." Journal of Chemical Theory and Computation 7(1):10-18. doi:10.1021/ct1005533
Suthirakun S, SC Ammal, G Xiao, F Chen, K Huang, HC zur Loye, and A Heyden. 2012. "Obtaining Mixed Ionic/Electronic Conductivity in Perovskite Oxides in a Reducing Environment: A Computational Prediction for Doped SrTiO3." Solid State Ionics 228:37-45. doi:10.1016/j.ssi.2012.09.013
Tishchenko O, R Li, and DG Truhlar. 2010. "Metal-Organic Charge Transfer Can Produce Biradical States and is Mediated by Conical Intersections." Proceedings of the National Academy of Sciences of the United States of America 107(45):19139-19145. doi:10.1073/pnas.1010287107
Valiev M, and SV Lymar. 2011. "Structural and Mechanistic Analysis through Electronic Spectra: Aqueous Hyponitrite Radical (N2O2-) and Nitrosyl Hyponitrite Anion (N3O3-)." Journal of Physical Chemistry A 115(43):12004-12010.
Wang D, M Valiev, and BC Garrett. 2011. "CH2Cl2 and OH? Reaction in Aqueous Solution: A Combined Quantum Mechanical and Molecular Mechanics Study." Journal of Physical Chemistry A 115(8):1380-1384. doi:10.1021/jp109287r
Wang T, H Yin, D Wang, and M Valiev. 2012. "Hybrid Quantum Mechanical and Molecular Mechanics Study of the SN2 Reaction of CCl4 + OH- in Aqueous Solution: The Potential of Mean Force, Reaction Energetics, and Rate Constants." Journal of Physical Chemistry A 116(9):2371-2376. doi:10.1021/jp3005986
Wen H, GL Hou, SM Kathmann, M Valiev, and XB Wang. 2013. "Communication: Solute Anisotropy Effects in Hydrated Anion and Neutral Clusters." Journal of Chemical Physics 138(3):Article No. 031101. doi:10.1063/1.4776766
Yin H, D Wang, and M Valiev. 2011. "Hybrid quantum mechanical/molecular mechanics study of the S(N)2 reaction of CH3Cl+OH? in water." Journal of Physical Chemistry A 115(43):12047-12052.
Zheng J, P Seal, and DG Truhlar. 2012. "Role of Conformational Structures and Torsional Anharmonicity in Controlling Chemical Reaction Rates and Relative Yields: Butanal + HO2 Reactions." Chemical Science. doi:10.1039/c2sc21090h