Computational Chemical Dynamics of Complex Systems

 

Funding and resources:

"Computational Chemical Dynamics of Complex Systems" is a Computational Grand Challenge project of The William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. Resources are provided by EMSL's Molecular Science Computing Facility (MSCF).
http://mscf.emsl.pnl.gov/research/intro_cgca.shtml

The project is a collaborative effort involving scientists in the Department of Chemistry at the University of Minnesota and scientists at PNNL.
 

Participants:

University of Minnesota           Donald Truhlar, Principal Investigator
  Aleksandr Marenich, Project Manager for UMN

John Alecu

Elizabeth A. Amin
  Boris Averkiev
  Alessandro Cembran
  Christopher Cramer
  Luke Fiedler

Laura Gagliardi

Jiali Gao
  Andreas Heyden (collaborator, University of South Carolina)
  Hannah Leverentz
  Hai Lin (collaborator, University of Colorado - Denver)
  Steven L. Mielke
  Ewa Papajak
  J. Ilja Siepmann

Oksana Tishchenko
  Ke Yang
  Jingjing Zheng
   
PNNL Marat Valiev, Project Manager for PNNL
  Peng-Dong Fan
  Bruce C. Garrett
  Karol Kowalski
  Sriram Krishnamoorthy
 
 

Project summary:

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. 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 are being carried out with new high-throughput integrated software that we are developing.

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 a variety of condensed-phase modeling problems including 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 are therefore carrying 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, are 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 are developing 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 are constructing potential energy surfaces for a number of photochemical reactions and employing them for dynamics calculations based on the new decay of mixing with coherent switches algorithm. We are also considering solvatochromic shifts on conical intersections that govern selected photochemical processes.

 
List of publications supported in part by Computational Grand Challenge grants (2007-2009:

  1. “Thermochemical kinetics of hydrogen-atom transfers between methyl, methane, ethynyl, ethyne, and hydrogen,” J. Zheng, Y. Zhao, and D. G. Truhlar, J. Phys. Chem. A 2007, 111, 4632.
  2.  “Attractive noncovalent interactions in Grubbs second-generation Ru catalysts for olefin metathesis,” Y. Zhao and D. G. Truhlar, Org. Lett. 2007, 9, 1967.
  3.  “Size-selective supramolecular chemistry in a hydrocarbon nanoring,” Y. Zhao and D. G. Truhlar, J. Am. Chem. Soc. 2007, 129, 8440.
  4.  “Hybrid approach for free energy calculations with high-level methods: Application to the SN2 reaction of CHCl3 and OH- in water,” M. Valiev, B. C. Garrett, M.-K. Tsai, K. Kowalski, S. M. Kathmann, G. K. Schenter, and M. Dupuis, J. Chem. Phys. 2007, 127, 051102.
  5.  “Molecular computational investigation of electron-transfer kinetics across cytochrome-iron oxide interfaces,” S. Kerisit, K. M. Rosso, M. Dupuis, and M. Valiev, J. Phys. Chem. C 2007, 111, 11363.
  6.  “Density functionals with broad applicability in chemistry,” Y. Zhao and D. G. Truhlar, Acc. Chem. Res. 2008, 41, 157.
  7. “A prototype for graphene material simulation: Structures and interaction potentials of coronene dimers,” Y. Zhao and D. G. Truhlar, J. Phys. Chem. C 2008, 112, 4061.
  8. “Density functional theory in transition-metal chemistry: relative energies of low-lying states of iron compounds and the effect of spatial symmetry breaking,” A. Sorkin, M. A. Iron, and D. G. Truhlar, J. Chem. Theory Comput. 2008, 4, 307.
  9. “How well can new-generation density functionals describe the energetics of bond dissociation reactions producing radicals?” Y. Zhao and D. G. Truhlar, J. Phys. Chem. A 2008, 112, 1095.
  10. “Benchmark data for interactions in zeolite model complexes and their use for assessment and validation of electronic structure methods,” Y. Zhao and D. G. Truhlar, J. Phys. Chem. C 2008, 112, 6860.
  11. “Computational characterization and design of buckyball tweezers: density functional study of concave-convex pi...pi interactions,” Y. Zhao and D. G. Truhlar, Phys. Chem. Chem. Phys. 2008, 10, 2813.
  12. “Perspective on foundations of solvation modeling: the electrostatic contribution to the free energy of solvation,” A. V. Marenich, C. J. Cramer, and D. G. Truhlar, J. Chem. Theory Comput. 2008, 4, 877.
  13. “Construction of a generalized gradient approximation by restoring the density-gradient expansion and enforcing a tight Lieb-Oxford bound,” Y. Zhao and D. G. Truhlar, J. Chem. Phys. 2008, 128, 184109.
  14. “Large-scale parallel calculations with combined coupled cluster and molecular mechanics formalism: excitation energies of zinc-porphyrin in aqueous solution,” P. D. Fan, M. Valiev, and K. Kowalski, Chem. Phys. Lett. 2008, 458, 205.
  15. “Exploring the limit of accuracy of the global hybrid density functional for main-group thermochemistry, kinetics, and noncovalent interactions,” Y. Zhao and D. G. Truhlar, J. Chem. Theory Comput. 2008, 4, 1849.
  16. “Benchmark energetic data in a model system for Grubbs II metathesis catalysis and their use for assessment and validation of electronic structure methods,” Y. Zhao and D. G. Truhlar, J. Chem. Theory Comput. 2009, 5, 324.
  17. “On the function of pentameric phospholamban: ion channel or storage form?” L. Becucci, A. Cembran, C. B. Karim, D. D. Thomas, R. Guidelli, J. Gao, and G. Veglia, Biophys. J. 2009, 96, L60.
  18. “Universal solvation model based on solute electron density and a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions,” A. V. Marenich, C. J. Cramer, and D. G. Truhlar, J. Phys. Chem. B 2009, 113, 6378.
  19. “Interactions of Cl- and OH radical in aqueous solution,” M. Valiev, R. D'Auria, D. J. Tobias, and B. C. Garrett, J. Phys. Chem. A 2009, 113, 8823.
  20. “Thermochemical kinetics for multireference systems: Addition reactions of ozone,” Y. Zhao, O. Tishchenko, J. R. Gour, W. Li, J. J. Lutz, P. Piecuch, and D. G. Truhlar, J. Phys. Chem. A 2009, 113, 5786.

Research highlights:
  
Computationally Intensive Research Project (2009-2011):
grant proposal (submitted: April 30, 2009; approved: October 1, 2009)

2007-2009 Final Report (Technical Section)
2007-2009 Final Report (PowerPoint Slides)
  
2008 Summary
2008 Technical Report
2008 PowerPoint Slides

2007 Summary
2007 Technical Report
2007 PowerPoint Slides
 

Additional information:
 
Additional research documents for internal use (password-protected)
Request for a Grand Challenge account (password-protected)  
 

Links:

Donald G. Truhlar's Home Page
Integrated Tools Home Page
Computational Chemistry at the University of Minnesota
Chemical Sciences Division, PNNL
Department of Chemistry at the University of Minnesota

This document last modified Monday, 02-Nov-2009 16:40:50 CST