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Fast and accurate reaction dynamics via multiobjective genetic algorithm optimization of semiempirical potentials
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Fast and accurate reaction dynamics via multiobjective genetic algorithm optimization of semiempirical potentials

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  • 1. The Materials Computation Center, University of Illinois Duane Johnson and Richard Martin (PIs), NSF DMR-03-25939 • www.mcc.uiuc.edu Fast and Accurate Reaction Dynamics via Multiobjective Genetic Algorithm Optimization of Semiempirical Potentials aKumara Sastry, bAlexis L. Thompson, cDuane D. Johnson, aDavid. E. Goldberg, bTodd J. Martinez aIndustrial and Enterprise Systems Engineering, bChemistry and Beckman Institute cMaterials Science and Engineering Silver Medal in Human Competitive Results at GECCO 2006 (ACM SIGEVO conference) Best paper award, Real-world applications track, GECCO-2006 (ACM SIGEVO conference) This work is supported by the Materials Computation Center (UIUC) NSF DMR 03-25939 and AFOSR FA9550-06-1-0096
  • 2. Modeling Photochemical Reactions Halorhodopsin Excited state Ground state Photochemistry important for photosynthesis, vision, solar energy Need an accurate Dynamics requires method that includes many evaluations of excited states the electronic energy
  • 3. Reaction Dynamics Over Multiple Timescales Ab Initio Semiempirical Quantum Chemistry Methods Methods Accurate but slow (hours-days) Fast (seconds-minutes) Can calculate excited states Calculate integrals from fit parameters Accuracy depends on parameters Origin of our collaboration: Can we use optimization methods to do this reliably? Can we get reasonable excited state surfaces with the speed of a semiempirical (SE) method? This would allow us to study the dynamics of much larger systems: solvated chromophores, proteins, nanotubes…
  • 4. Methodology: Limited Ab Initio Results to Tune Semiempirical Parameters Standard parameter sets don’t yield accurate potential energy surfaces (PESs) Example: AM1, PM3, etc. Parameterized for ground state properties Calculate excited states using a CI technique within a small set of optimized orbitals Parameter sets need to be reoptimized Optimize for a particular system, such as ethylene Fit to only a few important geometries for the molecule Maintain accurate description of ground-state properties Yield globally accurate PES (including excited states)
  • 5. Ethylene Test Case for Reparameterization twists excited pyramidalizes E ground Ethylene is the smallest molecule to show cis-trans isomerization Energetics of excited state involved pyramidalized intersection Semiempirical methods (AM1, PM3) do not reproduce this behavior Are they transferable? (Found for one system works for others.)
  • 6. Current Reparameterization Methods Fall Short; Need Multiobjective Optimization Current Method: Staged single-objective optimization First minimize error in energies Subsequently minimize weighted error in energy and gradient Multiple objectives and highly multimodal Don’t know the weights of different objectives Local search gets stuck in low-quality optima Multiobjective optimization Simultaneously obtain “Pareto-optimal” solutions. O Avoid potentially irrelevant O O * and unphysical pathways.
  • 7. Multiobjective Optimization Unlike single-objective problems, multiobjective problems involve a set of optimal solutions often termed as Pareto- optimal solutions. Notion of Non-Domination • A dominates C Solution A dominates C if: • A and B are non-dominant A is no worse than C in all objectives • B is more crowded than A A is better than C in at least one objective Two goals: Converge onto the Pareto-optimal solutions (best non-dominated set ) Maintain as diverse a distribution as possible
  • 8. Multiobjective Genetic Algorithms (MOGAs) Search method based on “evolutionary” principles Representation: GAs operate on codes Binary, gray, permutation, real, program Fitness functions: Relative quality measures of a solution Objective, subjective, co-evolutionary Population: Candidate solutions (individuals) Genetic operators: Selection: “Survival of the non-dominated” Recombination: Combine parental traits to create offspring Mutation: Modify an offspring slightly Replacement: Replace parents with offspring
  • 9. Fitness: Errors in Energy and Energy Gradient Choose few ground- and excited-state ab initio SE method configurations Fitness #1: Errors in energy For each configuration, compute energy difference via ab initio and semiempirical methods ab initio SE method Fitness #2: Errors in energy gradient For each configuration, compute energy gradient via ab initio and SE methods
  • 10. MOGA Finds Physical and Accurate PES MOGA vs Previously Each point is published a set of 11 results parameters MOGA results have significantly lower errors than current results. Globally accurate PES yielding physical reaction dynamics
  • 11. Multiobjective Optimization Is Efficient MOGA vs Multiple weighted single-objective GA runs Not even one Pareto-optimal solution obtained with multiple weighted single-objective optimizations
  • 12. Qualifying the Parameter Set Analyze the robustness of the parameter set Small changes in the parameters (0.1% or less) should have small effects on the error in energy and error in gradient Select ten parameters sets around each optimized parameter set and calculate error in energy and error in gradient for each set
  • 13. Eliminate Sensitive Parameter Sets (Manually) 1.0 1.0 0.9 0.9 Error in Energy Gradient (eV/Ang) Error in Energy Gradient (eV/Ang) 0.8 0.8 0.7 0.7 0.6 0.6 0.5 0.5 0.4 0.4 0.3 0.3 0.2 0.2 0.1 0.1 0.0 0.0 0 1 2 3 4 0 1 2 3 4 Error in Energy (eV) Error in Energy (eV) Remove points that have large RMSD values above 0.05 eV for error in energy above 0.008 eV/Ang for error in energy gradient
  • 14. On-Line Parameter Stability Analysis in MOGA GA population contains data that can be mined, e.g., sensitivity of parameter sets Analysis of quality of solutions around Pareto-optimal set yields a good measure of the SE parameter stability. More perturb points in the MOGA analysis – higher reliability!
  • 15. Check potential energy surface with dynamics 220 200 Time for 50% Population Transfer (fs) 180 160 ab initio value: 180±50 fs 140 120 100 80 60 40 20 0 0.42 0.44 0.46 0.48 0.50 0.52 0.54 0.56 0.58 0.60 Error in Energy Gradient (eV/Ang) Population transfer determined using 20 initial conditions for each parameter set Parameter sets with lower error in energy gradient values have lifetimes close to ab initio value J. Quenneville, M. Ben-Nun, T. J. Martinez, J. Photochem. Photobiol.,144, 229 (2001)
  • 16. Key Results Yields multiple parameter sets that are significantly higher quality than current published results. Significantly outperforms single-objective optimization Enables 102-105 increase in simulation time 10-103 times faster than current reparameterization method Population based search enables on-line sensitivity analysis Currently investigating transferability of the SE parameters Enables accurate simulation of complex reactions without complete reoptimization Pareto analysis using symbolic regression via GP Interpretable semiempirical potentials
  • 17. Outlook Broadly applicable in chemistry and materials science Analogous applicability in modeling multiscaling phenomena. Facilitates fast and accurate materials modeling Alloys: Kinetics simulations with ab initio accuracy. 104-107 times faster than current methods [Sastry, et al (2006), Phys. Rev. B*]. Chemistry: Reaction-dynamics simulations with ab initio accuracy.102-105 times faster than current methods. Lead potentially to new drugs, new materials, fundamental understanding of complex chemical phenomena Science: Biophysical basis of vision, and photosynthesis Synthesis: Pharmaceuticals, functional materials chosen by the AIP editors as focused article of frontier research in Virtual Journal of Nanoscale Science & Technology, 12(9), 2005
  • 18. Software Contribution Genetic algorithms suite in C++ Single & multiple objectives with and without constraints Array of selection, crossover, mutation, and other operators Optional interface with Matlab® Currently working on the documentation Other competent and efficient GAs (which acknowledge MCC) are available at http://www-illigal.ge.uiuc.edu and http://medal.cs.umsl.edu/software.php. Extended compact GA in C++, version 1.1 χ-ary extended compact GA in C++ χ-ary extended compact GA for Matlab in C++ Generator of random additively decomposable problems
  • 19. Connections to MCC’s Goals Cross-disciplinary collaborations Brought together a disparate, unique, and highly-qualified group to leverage expertise. Development of forefront algorithms Developed a novel method using MOGA that permits faster and reliable search of high-quality quantum-chemistry potentials. Development of extensible, user-friendly, open-source code Created a generic optimization and analysis code, which will be made available via Software Archive and IlliGAL sites. Enables analysis, understanding and prediction of properties Rapid and accurate simulation permits new science, synthesis, and facilitates bridging the gap between experiment and theory