Computational Chemical Dynamics of Complex Systems
EMSL Project ID
20893
Abstract
The goal of this project is to apply powerful new simulation techniques to tackle computationally challenging problems in chemical dynamics, with special emphasis on electrochemistry, heterogeneous catalysis, nanoparticles, solid-state dynamics, and photochemistry. These calculations will be carried out with new high-throughput integrated software that we are developing. New research capabilities in computational chemical dynamics are expected to play a significant role in enabling environmental scientists worldwide to address environmental challenges facing DOE and the nation. Recent advances in computer power and algorithms have made possible accurate calculations of many chemical properties for both equilibria and kinetics. Nonetheless, applications to complex chemical systems, such as reactive processes in the condensed phase, remain problematic due to the lack of a seamless integration of computational methods that allow modern quantum electronic structure calculations to be combined with state-of-the-art methods for chemical thermodynamics and reactive dynamics. These problems are often exacerbated by unvalidated methods and limited software reliability. Our consortium is developing an integrated software suite that combines electronic structure packages with dynamics codes and efficient sampling algorithms for the following kinds of condensed-phase modeling problems that we propose to tackle in various parts of the present Grand Challenge project: thermochemical kinetics and rate constants, photochemistry and spectroscopy, chemical and phase equilibria, electrochemistry, and heterogeneous catalysis. These fundamental areas of research are important for solar energy, fuel-cell technology, environmental remediation, weather modeling, pollution modeling, and atmospheric chemistry. Photochemical creation of excited states offers a means to control chemical transformations because different wavelengths of light can be used to create different vibronic states, thereby directing chemical reactions along different pathways. It is crucial to understand how energy deposited into the system is used; this is particularly complicated in condensed phase systems where there are many ways to dissipate excess energy. Similar opportunities and challenges present themselves in the areas of electrochemistry and catalysis. We therefore propose to carry out prototype large-scale applications on environmental problems as well as other applications to complex chemical dynamics processes, focusing on three high-impact areas. In the computational electrochemistry area, we will be especially concerned with processes that enhance the design of fuel cell technology and with the calculation of in situ reduction potentials. For heterogeneous, nanoparticle, and solid-state dynamics, we will develop an array of methods for multi-time-scale simulation of nucleation of crystals in solution, reactions of radicals at solution-phase interfaces and in ice, zeolite catalysis, structure and dynamics of gallazane precursors to gallium nitride nanocrystals, the regulatory role of metal ions in the reactivity of inorganic phosphates, nanoparticles structure and dynamics, and ice dynamics. In the computational photochemistry area, we will construct potential energy surfaces for a number of photochemical reactions and employ them for dynamics calculations based on the new decay of mixing with coherent switches algorithm. We will also consider solvatochromic shifts on conical intersections that govern selected photo chemical processes.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
Becucci L, A Cembran, CB Karim, DD Thomas, R Guidelli, J Gao, and G Veglia. 2009. "On the Function of Pentameric Phospholamban: Ion Channel or Storage Form?" Biophysical Journal 96(10):L60-L62. doi:10.1016/j.bpj.2009.03.013
Fan PD, M Valiev, and K Kowalski. 2008. "Large-Scale Parallel Calculations with Combined Coupled Cluster and Molecular Mechanics Formalism: Excitation Energies of Zinc-porphyrin in Aqueous Solution." Chemical Physics Letters 458(1-3):205-209.
Kerisit SN, KM Rosso, M Dupuis, and M Valiev. 2007. "Molecular Computational Investigation of Electron Transfer Kinetics across Cytochrome-Iron Oxide Interfaces." Journal of Physical Chemistry C 111(30):11363-11375.
Kowalski K, and M Valiev. 2008. "The Application of High-Level Iterative Coupled-Cluster Methods to the Cytosine Molecule." Journal of Physical Chemistry A 112(24):5538-5541.
Marenich A, CJ Cramer, and DG Truhlar. 2008. "Perspective on Foundations of Solvation Modeling: The Electrostatic Contribution to the Free Energy of Solvation." Journal of Chemical Theory and Computation 4(6):877-887. doi:10.1021/ct800029c
Marenich A, CJ Cramer, and DG Truhlar. 2009. "Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions." Journal of Physical Chemistry B 113(18):6378-6396. doi:10.1021/jp810292n
Sorkin A, MA Iron, and DG Truhlar. 2008. "Density Functional Theory in Transition-Metal Chemistry: Relative Energies of Low-Lying States of Iron Compounds and the Effect of Spatial Symmetry Breaking." Journal of Chemical Theory and Computation 4(2):307-315. doi:10.1021/ct700250a
Tsai MK, K Kowalski, M Valiev, and M Dupuis. 2007. "Signature OH Absorption Spectrum from cluster Models of Solvation: a solvent-to-solute charge transfer state." Journal of Physical Chemistry A 111(42):10478-10482.
Valiev M, BC Garrett, MK Tsai, K Kowalski, SM Kathmann, GK Schenter, and M Dupuis. 2007. "Hybrid Approach for Free Energy Calculations with High-Level Methods: Application to the S(N)2 Reaction of CHCl3 and OH- in Water." Journal of Chemical Physics 127(5):51102 (1-4).
Valiev M, R D'Auria, DJ Tobias, and BC Garrett. 2009. "Interactions of Cl- and OH Radical in Aqueous Solution." Journal of Physical Chemistry A 113(31):8823-8825.
Zhao Y, and DG Truhlar. 2007. "Attractive Noncovalent Interactions in the Mechanism of Grubbs Second-Generation Ru Catalysts for Olefin Metathesis." Organic Letters 9(10):1967-1970.
Zhao Y, and DG Truhlar. 2007. "Size-Selective Supramolecular Chemistry in a Hydrocarbon Nanoring." Journal of the American Chemical Society 129(27):8440-8442.
Zhao Y, and DG Truhlar. 2008. "A Prototype for Graphene Material Simulation: Structures and Interaction Potentials of Coronene Dimers." Journal of Physical Chemistry C 112(11):4061-4067. doi:10.1021/jp710918f
Zhao Y, and DG Truhlar. 2008. "Benchmark Data for Interactions in Zeolite Model Complexes and Their Use for Assessment and Validation of Electronic Structure Methods." Journal of Physical Chemistry C 112(17):6860-6868. doi:10.1021/jp7112363
Zhao Y, and DG Truhlar. 2008. "Computational characterization and modeling of buckyball tweezers: density functional study of concave–convex π•••π interactions." Physical Chemistry Chemical Physics. PCCP 10:2813-2818. doi:10.1039/b717744e
Zhao Y, and DG Truhlar. 2008. "Construction of a Generalized Gradient Approximation by Restoring the Density-gradient Expansion and Enforcing a Tight Lieb-Oxford Bound." Journal of Chemical Physics 128:184109/1-8. doi:10.1063/1.2912068
Zhao Y, and DG Truhlar. 2008. "Density Functionals with Broad Applicability in Chemistry." Accounts of Chemical Research 41(2):157-167. doi:10.1021/ar700111a
Zhao Y, and DG Truhlar. 2008. "Exploring the Limit of Accuracy of the Global Hybrid Meta Density Functional for Main-Group Thermochemistry, Kinetics, and Noncovalent Interactions." Journal of Chemical Theory and Computation 4(11):1849-1868. doi:10.1021/ct800246v
Zhao Y, and DG Truhlar. 2008. "How Well Can New-Generation Density Functionals Describe the Energetics of Bond-Dissociation Reactions Producing Radicals?" Journal of Physical Chemistry A 112(6):1095-1099. doi:10.1021/jp7109127
Zhao Y, and DG Truhlar. 2009. "Benchmark Energetic Data in a Model System for Grubbs II Metathesis Catalysis and Their Use for the Development, Assessment, and Validation of Electronic Structure Methods." Journal of Chemical Theory and Computation 5(2):324-333. doi:10.1021/ct800386d
Zhao Y, O Tishchenko, JR Gour, W Li, J Lutz, P Piecuch, and DG Truhlar. 2009. "Thermochemical Kinetics for Multireference Systems: Addition Reactions of Ozone." Journal of Physical Chemistry A 13(19):5786–5799. doi:10.1021/jp811054n
Zheng J, Y Zhao, and DG Truhlar. 2007. "Thermochemical Kinetics of Hydrogen-Atom Transfers between Methyl, Methane, Ethynyl, Ethyne, and Hydrogen." Journal of Physical Chemistry A 111(21):4632-4642.