August 2012 - Allocations-admins - mailman3.cels.anl.gov

[LCRC Accounts] Yearly Allocation Request from SOFC
by accounts＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Yuxin Wang Project Name: SOFC Division: XSD Project title: Imaging, Analysis and Simulation of Heterogeneous Functional Materials Associated funding: DoE Other Systems: Primarily workstations at present. Science: The DOE Energy Frontier Research Center (EFRC) on Heterogeneous Functional Materials for Energy Systems (HeteroFoaM Center), led by the University of South Carolina, is a collaboration with scientists at APS, University of Connecticut, Princeton University, University of Utah, the Georgia Institute of Technology, Rochester Institute of Technology, and the University of California-Santa Barbara. The central objective of this EFRC, funded by DOE-SC Office of Basic Energy Sciences, is to build a scientific basis for bridging the gap between making nano-structured materials and understanding how they function in a variety of energy applications (www.science.doe.gov/bes/EFRC/CENTERS/HeteroFoaM/efrc_HeteroFoaM.html) Energy devices such as fuel cells, electrolyzers, combustion and fuel processing devices consist of multiple materials interacting at multiple scales. Establishing a fundamental understanding of the functional behavior of these material systems at multiple length and time scales as the basis for providing a scientific foundation for the conceptual design, simulation and fabrication of nano-structured heterogeneous materials for energy systems is the objective of the EFRC. Central to this effort is the formulation of science-based theory and computational methods for the analysis and simulation of the functional performance of these materials based on their composition, configuration and nano-morphology. Central themes in understanding functional materials in non-equilibrium states involves understanding transport, conversion, transfer of mass, momentum, energy and charge, as well as stability and durability for long-term performance. The present proposal seeks the computational resources required for the reconstruction and analysis of materials imaged using a transmission x-ray microscope at APS beamline 32-ID-C. Structures, elemental and chemistry information obtained will be used to perform quantum chemical and mechanical, and mesoscale (phase-field and lattice Boltzmann) modeling and simulation of the non-equilibrium thermodynamics and diffusion/reaction kinetics at the atomic scale at interfaces in heterogeneous materials, stability of films as function of morphology, and predictive estimation of properties and functional behavior. The methodologies that will be applied include i) quantum-mechanical atomic level simulations to understand how materials behave at interfaces and as function of morphology, dopants, and nano-sized features, ii) mesoscale simulations to incorporate geometrical effects with atomic detail, iii) evaluation of new material properties, and iv) multiscale physics analysis of soli d oxide fuel cells (SOFCs). Project description: This project involves three Universities from the HeteroFoaM EFRC (www.heterofoam.com) Princeton University, University of Connecticut, and University of South Carolina. Project goals and achievements from the previous year are described below: (1) University of South Carolina: Project Title: Rational Design of Sulfur and Carbon Tolerant Anode Materials for Solid Oxide Fuel Cells Project Division: Energy Systems Select PIs and Members: Andreas Heyden, Muhammad Faheem, Suwit Suthirakun, Salai C. Ammal Funding Source: Department of Energy (BES) Award No. DE-SC0001061 (primary) and DE-SC0007167 (secondary) Abstract: The objectives of this project are (1) to develop a doping strategy for mixed ionic/electronic conductivity in perovskite oxides (and to try to understand the physical reasons for the “soup of elements” often found in practical electrodes for solid oxide fuel cells, SOFCs), (2) to understand the fuel oxidation process on the Sr2Fe1.5Mo0.5O6 (001) perovskite oxide surface and the Ni/YSZ (111) interface in the presence and absence of sulfur containing compounds, required for proposing design modifications of SOFCs, and (3) to develop realistic microkinetic models that can be used in, e.g., Lattice Boltzmann simulations to study HeteroFoaMs under operation in a SOFC over “longer” time and length scales. Finally, a limited amount of computer time will also be used to support our efforts to develop computational methodologies for modeling chemical reactions at solid-liquid interfaces relevant for catalytic lignocellulosic biomass conversion processes. New Results: (1) We illustrated that mixed p- and n-doping is an efficient strategy to obtain mixed ionic/electronic conductivity in perovskite oxides such as SrTiO3. Moreover, we have proven that this strategy is valid independent of n-doping site (A- or B-site) in the perovskite structure. Both, La (n-type) and Ga (p-type), and Nb (n-type) and Ga (p-type) doped SrTiO3 exhibit mixed ionic and electronic conductivity in a reducing environment as long as the concentration of p-dopants is significantly below, e.g., half, the concentration of the n-dopant. (2) We understand the rate / performance limiting step in SOFCs based on Sr2Fe1.5Mo0.5O6-δ (SFM) anodes running on H2. After identifying the surface phase of SFM (001) under anodic SOFC conditions with the help of constrained ab initio thermodynamic calculations, we studied the reaction mechanism of the electrochemical H2 oxidation from first principles, and developed a microkinetic model that clearly identified the H2 dissociation step to be rate determining. As a result, adding a transition metal to the SFM surface such as Ni facilitates H2 dissociation and improves the overall cell performance. Indeed, experimental observations from our collaborators confirm this predicted SOFC cell behavior. (3) We understand the reaction mechanism of the electrochemical H2 oxidation at the Ni/YSZ interface. The oxidation mechanism of H2 at the Ni/YSZ interface has been investigated considering the following pathways: (i) H-spillover pathway (H-spillover from Ni to YSZ where water formation occurs), (ii) OH-migration pathway (H-spillover from Ni to YSZ leading to OH species that spillover from YSZ to Ni where water formation occurs), and (iii) O-migration pathway (O-spillover from YSZ to Ni where H2O formation occurs). In all of these pathways H2 adsorbs dissociatively on Ni and reacts with an oxygen atom at the interface which leads to the formation of H2O and a surface vacancy. Analysis of a microkinetic model containing all three pathways led to the following conclusion: If we assume that the cathode reaction is fast, the apparent activation barrier for all three pathways are within the range of reported experimental values (100-135 kJ/mol). However, the highest rate (by t hree orders of magnitude) is predicted for the O-migration pathway. Project Impact: The vision of this research program strikes at the heart of the “Grand Challenges for Basic Energy Sciences” described in the BESAC report. The fundamental objective of this project is to create a scientific basis for the rational design of novel heterogeneous functional materials and their surfaces for applications to SOFCs, supercapacitors, etc. New Capabilities: 1) Implementation and testing of new physical models for electrochemical reactions on perovskite based SOFC anode electrodes. 2) Implementation and testing of new physical models for electrochemical reactions at the three-phase boundary of SOFC anode electrodes. 3) Implementation and testing of new physical models for reactions at solid-liquid interfaces. Publications: 1) S. Suthirakun, S. C. Ammal, G. Xiao, F. Chen, K. Huang, H.-C. zur Loye, A. Heyden, “Obtaining Mixed Ionic/Electronic Conductivity in Perovskite Oxides in a Reducing Environment: A Computational Prediction for Doped SrTiO3,” Solid State Ionics, under review. 2) S. C. Ammal, A. Heyden, “Combined DFT and Microkinetic Modeling Study of Hydrogen Oxidation at the Ni/YSZ Anode of Solid Oxide Fuel Cells,” J. Phys. Chem. Lett., under review. 3) M. Faheem, S. Suthirakun, A. Heyden, “Implicit Solvation Model for Solid Surfaces,” J. Phys. Chem. C, under review. Presentations: 1) “SrTiO3 based Anode Materials for Solid Oxide Fuel Cells: A Computational Attempt to understanding and Improving Performance,” S. Suthirakun, A. Heyden, AIChE Annual Meeting, Minneapolis, MN, October 2011. 2) “Development and Application of a Hybrid QM/MM Method for the Computational Investigation of Reactions at Metal/Water Interfaces,” M. M. Faheem, A. Heyden, AIChE Annual Meeting, Minneapolis, MN, October 2011. 3) “Theoretical Investigation of Heterogeneous Catalysis at the Solid-Liquid Interface for the Conversion of Lignocellulosic Biomass Model Molecules,” A. Heyden, 2011 DOE-BES Catalysis Science PI Meeting, Annapolis, MD, October 2011. 4) “Density Functional Theory Study on the Electronic Structure of n- and p-type doped SrTiO3 as Anode for Solid Oxide Fuel Cells,” S. Suthirakun, S. C. Ammal, A. Heyden, Southeastern Catalysis Society Meeting, Asheville, NC, September 2011. Grants: 1) Department of Energy (BES) Award No. DE-SC0001061 (this is the main grant for the work done at ANL Fusion) 2) Department of Energy (BES) Award No. DE-SC0007167 (selected calculations have been performed at ANL Fusion for this catalysis grant) (2) Princeton University Using the LCRC computing resources, our group is investigating oxygen vacancy formation in solid oxide fuel cell cathode materials. We use accurate first-principles quantum mechanics calculations to provide insight into the fundamental processes that govern oxygen ion transport in these materials. Specifically, fundamentally understanding oxygen transport in mixed ion-electron conducting cathode materials will enable rational design of higher performance devices. We are calculating oxygen migration pathways within LaCoO3 explicitly accounting for quantum mechanical effects related to electron spin. Additionally, thermal effects arising from phonon dispersions may be important in determining accurate oxygen vacancy formation energies. These demanding calculations necessitate substantial computer time, and we have begun using LCRC resources to this end. LCRC support has resulted in a graduate student poster presentation (ECS, Boston, October 2011) and oral presentation (A CS, San Diego, March 2012) at national scientific meetings over the past fiscal year. Conference Presentations A. M. Ritzmann and E. A. Carter, "Ab initio DFT+U investigation of oxygen diffusion in solid oxide fuel cell materials La1-xSrxFeO3 and La1-xSrxCoO3," ACS Spring 2012 National Meeting & Exposition (Presentation Only), San Diego, CA. March 2012. A. M. Ritzmann and E. A. Carter, "First-Principles Quantum Mechanics Assessment of Oxygen Diffusion in La1-XSrXMO3 (M=Fe, Co) Based Materials," 220th ECS Meeting & Electrochemical Energy Summit (Poster Only), Boston, MA. October 2011. (3) University of Connecticut Wilson K. S. Chiu and William M. Harris Department of Mechanical Engineering University of Connecticut wchiu(a)engr.uconn.edu Microstructural imaging techniques, such as x-ray nanotomography and FIB serial sectioning, are able to provide detailed descriptions of solid-state energy materials at spatial resolutions appropriate for their structure and performance. However, to obtain a quantitative description of these materials, and thus determine their suitability for use in an energy-conversion device, requires a detailed description of the material microstructure. Characterization routines have been implemented on FUSION to analyze structures on the sub-micron scale with respect to such metrics as porosity, tortuosity, specific surface area, and phase contiguity. This analysis has been further extended to consider the relative distribution of different phases within a composite material, such as the Ni-YSZ anode commonly used in solid oxide fuel cell anodes. Furthermore, this characterization has been used as a foundation for more detailed simulations, such as the transport of gases within a dis crete porous structure. The complexity of these structures prevents the possibility of analysis on even a high-end desktop workstation, making the implementation on a machine such as FUSION essential. Publications: L. Zhang, N. Xu, X. Li, S. Wang, K. Huang, W. H. Harris and W. K. S. Chiu, “High CO2 Permeation Flux Enabled by Highly Interconnected Three-Dimensional Ionic Channels in Selective CO2 Separation Membranes,” Energy & Environmental Science, vol. 5, pp. 8310-8317, 2012. G. J. Nelson, K. N. Grew, J. R. Izzo, Jr., J. J. Lombardo, W. M. Harris, A. J. Cocco, A. Faes, A. Hessler-Wyser, J. Van herle, Y. S. Chu, S. Wang, A. V. Virkar and W. K. S. Chiu, “Three-Dimensional Microstructural Changes in the Ni-YSZ Solid Oxide Fuel Cell Anode During Operation,” Acta Materialia, vol. 60, pp. 3491-2500, 2012. J. J. Lombardo, R. Ristau, W. H. Harris and W. K. S. Chiu, “Focused Ion Beam Preparation of Samples for X-ray Nanotomography,” Journal of Synchrotron Radiation, vol. 19, pp. 789-796, 2012. W. M. Harris, G. J. Nelson, A. M. Kiss, J. R. Izzo, Jr., Y. Liu, M. Liu, S. Wang, Y. S. Chu and W. K. S. Chiu, “Nondestructive Volumetric 3-D Chemical Mapping of Nickel-Sulfur Compounds at the Nanoscale,” Nanoscale, vol. 4, pp. 1557-1560, 2012. Conference papers W. H. Harris, G. J. Nelson, J. J. Lombardo, A. P. Cocco, J. R. Izzo, Jr., W. K. S. Chiu, P. Tanasini, J. Van herle, C. Comninellis, J. C. Andrews, Y. Liu, P. Pianetta, and Y. Chu, “Analysis of Solid Oxide Fuel Cell LSM-YSZ Composite Cathodes with Varying Starting Powder Sizes,” Proceedings of the ASME 2011 International Mechanical Engineering Congress & Exposition, Paper No. IMECE2011-64237, Denver, CO, November 11-17, 2011. Project URL: http://www.science.doe.gov/bes/EFRC/CENTERS/HeteroFoaM/efrc_HeteroFoaM.html Current FY Hours Used: undetermined amount New FY Requested allocation: 800000 Q1: 200000 Q2: 200000 Q3: 200000 Q4: 200000 Justification: Image processing All image processing will be performed using Matlab. We will reconstruct an average of 20 samples per week requiring an average of 48 node hours per calculation (50,000 node hours per year). We will also be performing additional image processing of each sample requiring approximately 50 node hours per calculation (50,000 node hours per year). All calculations will require up to 400 GB of memory. Quantum chemical simulations and Quantum mechanical calculations Our DFT calculations will be performed using the Vienna Ab Initio Simulation Package (VASP) which solves the Kohn-Sham equations subject to periodic boundary conditions using a planewave basis set. We will perform an average of 50 single-point energy calculations each week requiring an average of 48 node hours per calculation (99,840 node hours per year). We will also be performing an average of 3 nudged elastic band calculations each week requiring approximately 1,500 node hours per calculation (234,000 node hours per year). All PEECM calculations will be performed with the Turbomole code (based on Gaussian-type basis sets) using hybrid and double-hybrid density functionals. Transition states required for the calculation of reaction rates will be located with our own highly efficient growing string and improved dimer algorithms. Recent tests on EMSL Chinook confirmed that both VASP and Turbomole scale well up to hundreds of nodes. Overall, we expect that computations required for quantum chemical calculations on the anode side of the SOFC will require approximately 750,000 node-hours per year and 500 GB of memory. This estimate is based on submitting 150 geometry optimizations and 20 transition state searches per year for each the perovskite and double perovskite structures (optimization of a perovskite structure requires on FUSION about 5000 node hours; optimization for a double perovskite structure requires about 12,500 node hours; transition state searches require about 10 times more time than a structure optimization). Phase-field Simulations Our continuum PF simulations will be performed with a parallel MPI code written in-house. While we have not benchmarked this particular code, our experience with similar codes in the past suggests that it should scale well up to 32 or 64 CPUs on the FUSION system. Furthermore, we estimate that a simulation with 1283 (2563) grid points will require 240 (1920) node-hours wall clock time and 100 GB (800GB) of memory. On an annual basis, we expect that our simulations of SOFC anode microstructural evolution phenomena require on the order of 200,000 node hours and 1 TB of memory on the FUSION system, corresponding to 100 high-resolution simulations. Lattice Boltzmann Calculations Our LBM simulation of 3D mass transport and electrochemistry in solid oxide fuel cells scales well up to 64 CPU on a local SGI Altix 850 system. For the FUSION system, we estimate that a single case using low resolution 813 lattice will require 350 node-hours wall-clock time and 100 GB memory on the FUSION system. A high resolution 6743 lattice will enable us to simulate realistic physical domain sizes and lead to better accuracy of the model predictions, but each case will require 22,400 node-hours wall-clock time and 1 TB memory on the FUSION system. Our annual estimated EFRC project needs on the FUSION system are 300,000 node hours: two low resolution lattice cases per week (36,400 node-hours wall-clock time per year), and one high resolution lattice case per month (268,800 node-hours wall-clock time per year). Summary of Computing Resource with Software, Node Hours, and Storage GB needs: Image Processing: Matlab, 50,000 node-hour, 400 GB Quantum chemical simulations: Turbomole, 140,000, 1,000 GB Quantum mechanical calculations: VASP, 358,800 node-hour, 1,500 GB Phase-field simulations: Intel C++ Compiler, 200,000 node-hour, 1000 GB Lattice Boltzmann calculations Intel Fortran Compiler: 50,000 node-hour, 1,500 GB Total: 798,800 node-hour, 5,400 GB Thank You, The LCRC Accounts System

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[LCRC Accounts] Yearly Allocation Request from Bubble
by accounts＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Zeke Insepov Project Name: Bubble Division: MCS, NE Project title: Multi-scale simulation of bubbles in nuclear fuels Associated funding: RERTR, AFCI, Argonne LDRD, NEAMS Other Systems: Blue Gene, WS Science: Summary of the project: Emission of energetic fission gases heavily damage nuclear fuels that leads to radiation cascade generation, amorphization, defect formation, lattice swelling, cracking and eventually to failure. Our simulation will be directed toward understanding these and other phenomena. Chemical and physical studies of cavity and vapor-gas filled bubble formation in metals have been conducted with continuum mechanics formulations in conjunction with empirically-derived equations of state. The condensation-evaporation phenomena at liquid-gas interface, dissociation and ionization phenomena which can occur during super compression and super heating for complex molecules has not been possible to assess on a molecular dynamics scale. DFT Ab-initio and classical molecular dynamics simulations will be performed for a number of points of the phase diagram region corresponding to the transient conditions the liquid-bubble interface experiences during the super-compression cycles. The formation of defects in bcc Mo lattice as a result of 50-keV Xe ion bombardment will be studied via atomistic simulation with an interatomic potential developed using the force-matching Ab initio based approach. Radiation defect formation via nuclear stopping power and evolution of the defects in the cascade will be described. Diffusion and interaction of interstitials and vacancies will be analyzed. Project description: computational methods: DFT vasp AND POTFIT codes, Molecular Dynamics and kinetic Monte Carlo simulations will used programming model: parallel experiments planned: Argonne IVEM and Atlas experiments software requirements: C++, fortran compiler (e.g. openmpi) sizes of calculations run on and/or planned for LCRC or other systems: hundreds of nano-seconds time scale MD simulations on 1e6-1e8 atomic systems expected number of project members: 9 We expect a total of 9 project members (three from Purdue University, one from the University of Illinois, and two from the JIHT in Moscow). Results of assessments are expected to lead to joint proposals to Argonne LDRD Strategic initiative, NSF, DOE (Office of Science, and NE), and DARPA, two applications were submitted to obtain International funding. Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 200000 Q1: 50000 Q2: 50000 Q3: 50000 Q4: 50000 Justification: Thank You, The LCRC Accounts System

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[LCRC Accounts] Yearly Allocation Request from radix
by accounts＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Robert Latham Project Name: radix Division: MCS Project title: Scalable Parallel System Software Associated funding: DoE core, SciDAC, NSF, FASTOS Other Systems: breadboard (unlimited) ALCF Intrepid/Surveyor (5,000,000 cpu hours) Science: Our mission is to develop the technologies required to dramatically increase the productivity of scientists developing applications for parallel supercomputers. The focus is fourfold: integration of parallel programming tools, reuse of parallel program components, development of scientific computing toolkits and portable libraries, and exploration of requirements of future parallel computers. Project description: This is a Computer Science request for 49,500 cpu-hours on Fusion for development and evaluation of a family of tools and libraries with a direct benefit to all users of high-performance computing resources. The Radix group in Argonnne's Mathematics and Computer Science division conducts research and development on facilities to better enable efficient Parallel Programming, I/O, and Scientific Understanding. The Fusion system represents an attractive milestone for our software development: projects start out on our breadboard cluster and can further explore scalability in the presence of a high speed network on Fusion before making the jump to BlueGene-scale parallelism. Radix experiments often are concerned with latency. The infiniband network on Fusion provides an excellent low-latency environment for message passing and storage management research while also providing ample bandwidth for I/O and message bandwidth testing. For FY2013 our Messaging middleware experiments include the usual MPICH2 development. We will study the continued improvement of various MPI features including scalability and memory usage, performance tuning, high-level libraries on top of MPI, fault tolerance capabilities, one-sided communication, and collective operations. This allocation will also be used for studying MPI extensions including active messages, and compiler support for MPI refactoring. We also plan for developing application-oriented libraries like ADLB, a load-balancing library. We will port the ADLB load-balancing library to Fusion and test its ability to function with multi-core nodes at intermediate scale, taking advantage of the multiple cores to replace MPI communication with local shared memory. The NWChem library will continue to improve the performance of an important scientific application that is widely used for science by Argonne researchers. Specifically, we will develop inspect-executor load-balancing techniques that will reduce network contention and improve the overall performance and scalability of an important family of methods (coupled-cluster methods). Furthermore, we will explore hybrid programming models (that is, adding threading to the existing GA/ARMCI/MPI model), particularly in the TCE module, which has been used extensively by researchers in Argonne MSD and CSE. All the aforementioned developments will be deployed on Fusion in a production fashion and made available to all users. This allocation will enable Jeff Hammond to maintain the NWChem installations on Fusion, as he has done since the machine went live. We work closely with application scientists, and develop application tools under the 'radix' allocation. For one example, the KMI project defines a high-level standardized interface for computational biology applications relying on distributed search and match semantics for biological reads. We will study efficient data management and data movement techniques to allow scaling to large number of processes. Fusion hosts two quality parallel file systems, GPFS and PVFS. The wider HPC community often asks the Radix file system researchers to compare these file systems head-to-head. Fusion provides us the opportunity to do just that. For FY 2013 our file system research extends into data storage approaches suitable for exascale. Our research into object storage protocols, including high performance access and replication, fits well on Fusion, with the large amount of local storage on compute nodes. Our Exascale storage efforts will explore scalable algorithms for use in next generation HPC storage systems. The Fusion allocation will be used to evaluate programming models, fault detection algorithms, synchronization primitives, and fault tolerance strategies for a prototype object storage system. Our NoLoss project explores how to integrate in-system storage in the I/O software stack. Under the NoLoss project, an abstraction layer for in-system storage was developed. The SCR checkpointing library was modified to store checkpoints locally using this newly developed abstraction layer. The fusion allocation will be used to explore the performance characteristics of this new approach. Hosting two parallel file systems allows us to do more than just drag-race (so to speak). The two file systems have distinct characteristics, and act differently in the broader role of the I/O software stack. On Fusion, we can utilize a single software stack (application, parallel-netcdf, ROMIO), and compare the impact of a change in the underlying file system on overall application behavior. We know from other research, for example, that the two-phase optimization in ROMIO needs to adapt to the underlying file system, and that aligning variables to file system boundaries can yield performance improvements for parallel-netcdf. In FY 2013 we are continuing research into new high level I/O libraries. We anticipate Fusion and Surveyor will be our two main test platforms. Fusion compute nodes actually look fairly attractive to active storage research. These nodes have enough disk space to store non-trivial datasets, and powerful enough processors to carry out complex computations without much impact on storage performance. Radix projects also focus on deriving insight both about application behavior as well as scientific insight. 8 core nodes make efforts like in-situ visualization, where for example an application renders a frame of a movie, ever more feasible. Even without fancy graphics accelerators, the processing power on Fusion nodes makes such analysis and visualization feasible, especially if the visualization can take advantage of multiple cores and multiple nodes. Naturally, the radix visualization tools have demonstrated scalability to Fusion sizes and beyond on Blue Gene, so making full utilization of Fusion should not be a concern. As should be evident from the variety of planned experiments, the Radix group plans to make full use of Fusion. With Argonne employees and student collaborators, we expect around 20 members in FY2013. We plan on about 0% of our jobs being single core jobs. It's crazy that you even have to ask! While Fusion may contain a modest number of compute nodes, the machine still represents an attractive platform for testing: very fast, low latency interconnect; 8 cores per node; .25 TB of storage per compute node. The testing and experiments the Radix group can carry out on Fusion ensures the tools the group develops today will remain relevant even as supercomputers grow. Quite a few radix-developed projects are part of the Fusion software stack: CPU hours for this project yield improvements and benefits not just for the radix group, but for all users of Fusion and indeed users of high-end computational resources worldwide. Project URL: http://www.mcs.anl.gov/research/group_detail.php?id=1 Current FY Hours Used: undetermined amount New FY Requested allocation: 49500 Q1: 12375 Q2: 12375 Q3: 12375 Q4: 12375 Justification: Thank You, The LCRC Accounts System

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New LCRC report submitted for Dissolution
by support＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Full project report at https://accounts.lcrc.anl.gov/reporting/project/2012/?project=Dissolution

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[LCRC Accounts] Yearly Allocation Request from HPCC
by accounts＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Amit Sharma Project Name: HPCC Division: CSE Project title: Ab-initio chemical kinetics study of high pressure combustion: A theoretical study of the radical-complex mechanism. Associated funding: Department of Energy Other Systems: Two small clusters (named: Pople and Linus) in the CSE fundamental interaction theory group. Science: Experimental investigation of the falloff curve for methyl radical oxidation, high-pressure addition reaction experiment of CCl3 with Br and benzyl radical self-addition show unexpected rise in rate constant at high pressures. In case of methyl oxidation the reaction is pressure dependent and high-pressure limit is achieved around 100 bar. Above 300 bar and in the 300 to 400 K temperature range, contribution from the radical-complex (RC) mechanism in addition to the usual energy-transfer (ET) mechanism is believed to be the dominant factor for this phenomena. The radical-complex mechanism, which has not been theoretically studied and quantified, is the formation of the radical-bath gas (R-M) complex and the stabilization/complexation is related to the strength of the R-M bond in the van der Waals complexes. The decomposition of this R-M complex to stabilized reactants yields an increase in the net association rate. Recently we have concluded the first part of our research in which we derived the rate expression for calculating radical-complex reaction rates. We developed codes to compute reaction rates at high-pressures. Project description: Following the conclusion of our CH3+O2 study (journal paper in preparation), we wish to test our theory on other systems such as CCl3+Br reaction and benzyl+benzyl reaction. These two reactions show similar high-pressure rise in rate coefficient. CCl3+Br is challenging due to spin-orbit effects. The addition reaction has 12 spin orbit electronic states of which two are attractive. We plan to calculate high pressure limiting rate on the ground spin-orbit electronic state using variable reaction coordinate transition state theory (VRC-TST). The VRC-TST calculations are expensive due to direct Monte-Carlo transition mode integrals. We compute, on-the-fly, multi reference electronic structure energies at CASPT2/aug-cc-pVDZ level of theory for sampled molecular configuration at a fixed value of reaction coordinate. In order to fit a full dimensional potential energy surface we compute thousands of such configurations spanning a multi-dimensional configuratio n space. We use MOLPRO code package for electronic structure energies. The VRC-TST code used for the calculation of reaction rate has been developed locally. The electronic structure dataset for fitting analytical PES consists of 40,000 to 50,000 electronic structure calculations for each pair of reactants. The computational cost of each electronic calculation depends on the size of the basis set, electronic structure methods and other auxiliary routines such as integral calculations and i/o routines. This can vary anywhere between 0.5 hours to couple of hours for a single point calculation, for the system we propose to study. There will be 1 to 2 people working on this project who will be using the computational resources. About 20% of the allocation will use non-parallel computations. This year we will work on CCl3+Br system and on benzyl+benzyl reaction. Benzyl is a resonance-stabilized structure and benzyl+benzyl addition reaction could require many cpu-hours. A 10 electron 6 orbital MCSCF/CASPT2/DZ test calculation, for example, requires few thousands of seconds on Pople cluster (quad core AMD opteron 1.1GHZ). However, any serious attempt to compute rate constant for this reaction would require use of a larger basis and perhaps a larger active space. We anticipate the need for longer cpu-hours especially for benzyl+benzyl reaction. Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 200000 Q1: 50000 Q2: 50000 Q3: 50000 Q4: 50000 Justification: Thank You, The LCRC Accounts System

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[LCRC Accounts] Project Request: ECG_LiAir
by accounts＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Hello, A new project on the LCRC cluster has been requested. Please forward the information on to the LCRC Allocation sub-committee. Applicant's name: Mike Welland Applicant's institution: ANL Applicant's division: MSD Project Name: ECG_LiAir Project title: Mesoscale modeling of electrochemical crystal growth for Li-air batteries Associated funding: Atomistically Informed Mesoscale Modeling for Advanced Electrical Energy Storage Systems Other Systems: Science: In this project, we preform mesoscale simulations of oxide growth in Li-air batteries by modeling multicomponent mass transport, electrostatics, structural mechanics, and microstructure evolution. The Theory of Irreversible Processes is applied to the material’s free energy functional to derive a system of highly coupled, non-linear set of partial differential equations, which are solved numerically using the finite element method. The phase-field model is used to account for the phase change. The study encompasses electrochemical crystal growth / dissolution as well as nanoscopic interfacial effects such as the electric double layer. In application to realistic systems, we seek to understand the factors influencing the performance, longevity and behavior of Li-air and similar advanced battery concepts. This work encompasses electrochemical crystal growth / dissolution as well as mesoscapoic effects such as the electric double layer. Project description: The derivation of the equations begins with a thermodynamic description of the system as a functional of the concentration of ionic species (Li+, O2-, A- and e-), the electrostatic potential, the local phase, and the strain. Working through the principles of entropy production, we can describe the electrochemical growth / dissolution process in a highly non-linear but nonetheless self-consistent system of at least seven partial differential equations. The system of coupled equations is solved numerically using the finite element solver platform MOOSE (Multiphysics Object Oriented Simulation Environment). MOOSE offers a real-space finite element solver and has been demonstrated to operate well on massively parallel architectures (1,2). One of its strengths is its use of the LibMesh and PETSc libraries for calculations, both widely recognized for their scalability and robustness. The solver method is the preconditioned Jacobian Free Newton Krylov solver, which scales well in parallel due to its avoidance of explicit calculation of the sparse Jacobian matrix. MPI is used to communicate between nodes. Complete consideration of the physics of the system, namely curved excess surface energies which can drive microstructure evolution, requires a 3-dimensional implementation. Due to the high resolution required by the phase-field model to accurately represent the phase boundary, problems of this sort are computationally expensive. It is this feature, and the non-linear nature of the problem, which motivates running this code on high performance computers in order to obtain results of sufficient size to be practically important within a reasonable timeframe. 1. D. Gaston, C. Newman, G. Hansen, and D. Lebrun-Grandie. MOOSE: A parallel computational framework for coupled systems of nonlinear equations. Nucl. Engrg. Design, 239:1768–1778, 2009. 2. R. Podgorney, H. Huang, and D. Gaston. Massively parallel fully coupled implicit modeling of coupled thermal-hydrological-mechanical processes for enhanced geothermal system reservoirs. In Proceedings, 35th Stanford Geothermal Workshop, Stanford University, Palo Alto, CA, Feb 1-3 2010. Project URL: http://cmcsn.phys.washington.edu/content/computational-microstructure-scien… Requested allocation: 400000 Q1: 50000 Q2: 100000 Q3: 100000 Q4: 150000 Justification: The requester has used undetermined amount hours of their initial startup project. In addition to approving an initial amount, please specify a Category and Subcategory for this project. For a list of the current selection of approved categories, please see: https://wiki.lcrc.anl.gov/wiki/Processes/Categories Once the Allocation committee has approved the project, please go to the Project Management page to create it: https://accounts.lcrc.anl.gov/projects.php Thank You, The LCRC Accounts System

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New LCRC report submitted for uncertainty-climate
by support＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Full project report at https://accounts.lcrc.anl.gov/reporting/project/2012/?project=uncertainty-c…

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[LCRC Accounts] Yearly Allocation Request from MBM
by accounts＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: hakim iddir Project Name: MBM Division: MSD Project title: Modeling Battery Materials (MBM) Associated funding: EFRC, EERE Other Systems: EMSL-PNNL, CNM-ANL Science: Rechargeable Li-ion batteries (LIB) have become one of the most important energy storage devices for portable electronics, electric and plug-in hybrid vehicles, owing to their high energy density and design flexibility 1. Graphitic based materials are usually used for the anode in commercial LIB because of their low cost, relatively high capacity, non-toxicity, and improved thermal stability and safety over lithium metal anodes2-5, as a result of a passivation film (solid-electrolyte interface (SEI)) that forms on graphite6. Previous studies suggested that defects in disordered/amorphous graphene sheets might be at the origin of their greatly enhanced storage capacity5,7,8. A fundamental understanding of both SEI formation, structure and properties, as well as Li and Li+ diffusion across different defects in graphene planes is a prerequisite to better understand the overall capacity and transport behavior of several graphitic anode materials and configurations in LI B, such as carbon nanospheres 9, carbon nanotubes (CNT)10, highly oriented pyrolitic graphite and graphene paper11. This work will be closely coupled with extensive experimental efforts conducted by two groups from the Chemical Sciences and Engineering (CSE) division, as well as research groups from Northwestern University (NU) and the University of Illinois at Urbana-Champaign (UIUC). This project is being done as part of the ANL EFRC on energy storage and an EERE funded program. (1) Tarascon, J. M.; Armand, M. Nature 2001, 414, 359. (2) Noel, M.; Santhanam, R. Journal of Power Sources 1998, 72, 53. (3) Fauteux, D.; Koksbang, R. Journal of Applied Electrochemistry 1993, 23, 1. (4) Yazami, R.; Touzain, P. Journal of Power Sources 1983, 9, 365. (5) Yoo, E.; Kim, J.; Hosono, E.; Zhou, H.-s.; Kudo, T.; Honma, I. Nano Letters 2008, 8, 2277. (6) Aurbach, D. Journal of Power Sources 2003, 119-121, 497. (7) Pan, D.; Wang, S.; Zhao, B.; Wu, M.; Zhang, H.; Wang, Y.; Jiao, Z. Chemistry of Materials 2009, 21, 3136. (8) Sato, K.; Noguchi, M.; Demachi, A.; Oki, N.; Endo, M. Science 1994, 264, 556. (9) Pol, S. V.; Pol, V. G.; Sherman, D.; Gedanken, A. Green Chemistry 2009, 11, 448. (10) Frackowiak, E.; Béguin, F. Carbon 2002, 40, 1775. (11) Abouimrane, A.; Compton, O. C.; Amine, K.; Nguyen, S. T. The Journal of Physical Chemistry C, 114, 12800. Project description: We propose to investigate the above mentioned properties (SEI formation, structure, Li transport, and reactions at the interface) on model systems using density functional theory (DFT) as implemented in the Vienna Ab Initio Simulation Package (VASP) currently available on FUSION. We have performed several studies of system size/shape dependence Li diffusion through defects in graphite/graphene as well as EC (solvent molecules) interaction with Au(111) and Cu(111) surfaces as part of this project (MBM) using the initial allocated time on Fusion. Recent results suggest that not only EC molecule but reduced (EC+Li) molecule in both open and closed ring configurations should be considered to investigate the SEI growth on Au, Cu and Sn surfaces. Further studies will require adding up to 3 EC (and ECLi) molecules to the most stable adsorbed configurations on Au,Cu and Sn. Frequency calculations will be performed on the resulting most stable configurations to link to the SFG experimental work performed by our EFRC collaborators at UIUC. Also within our EFRC work on battery materials and in collaboration with the experimental group at NU, we will continue to investigate the origin of capacity dependence on the electronic properties of carbon nanotubes (CNT) (We have just started some preliminary calculations on these systems). In this part of the project we will investigate the binding of Li to CNT(20,0) and CNT(11,11) (~1.5 nm diameter 240 and 220 C atoms, respectively) pristine surfaces as well as partially covered CNT surfaces (for example OH) resulting from mild acid treatments of the CNTs. Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 800000 Q1: 200000 Q2: 200000 Q3: 200000 Q4: 200000 Justification: The study of solvent molecules interaction with surfaces with frequency calculations will require the investigation of about 20 different configurations per solvent molecule and surface models. For each couple solvent/surface system about 50000 hours would be needed, we anticipate the investigation of EC/Au, EC/Cu, EC/Sn as well as ECLi/Au, ECLi/Cu and ECLi/Sn systems and adding at least one EC (or ECLi) to the most stable configuration for each system above to model the initial SEI growth. We will need about 500000 core hours would be necessary to complete this part of the project. The work on CNTs will require a total of 300000 core hours, Several Li coverage values will be considered (4 values: 0 limit, 0.1, 0.2, 0.5) on each CNT, other configurations of Li inside the CNTs will also be considered. Li binding between Metallic-Semiconducting (M-S), M-M, S-S, CNT pairs will be investigated. A total of about 800000 core hours would be needed to complete this project. Thank You, The LCRC Accounts System

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[LCRC Accounts] Yearly Allocation Request from intermetallic
by accounts＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Randall Meyer Project Name: intermetallic Division: CSE Project title: Fundamental studies of disparate metals in p/d alloys Associated funding: NSF Other Systems: NCSA 100,000 hr/yr Science: The project will use the VASP (Vienna Ab Initio Simulation Package) code to study the formation of unique phases in nanoalloys. Experimentally our group is working with Jeff Miller and Chris Marshall to synthesize alloy nanoparticles involving a d-band transition metal and a "p-electron" metal such as Ga, Ge or Sn. One interesting aspect of these alloys is that they form intermetallics as opposed to homogeneous alloys. However, it is not known how surface segregation may manifest itself in these systems. The primary aim of the proposed theoretical work is to understand the thermodynamics of nanoparticles relative to bulk phases in an effort to understand how to improve catalyst selectivity. Project description: The project has moved in two directions simultaneously over the last year. The first portion of the project focuses upon changes in the XANES spectra upon alloying. Previously we had examined the simulated XANES of PdPt alloys using CASTEP and found that changes in orbital overlap led to an broadening of the PDOS of Pd (now overbonded) and a narrowing of the PDOS of Pt (now underbonded). Alloying Pd with Ni shows the same shift in the absorption edge from that observed for PdPt although one might expect that the shifts should be different. As the shifts in PdNi mirror those of PdPt, this would suggest that the driving force must actually be different (since obviously we would initially expect 3d and 5d metals to have opposite effects on Pd). Simulated Pd/Ni PDOS for Pd and PdNi bulk shows that upon alloying of a 4d metal (Pd) with a smaller 3d metal there is a predicted narrowing of the d-band in the Ni and simultaneous broadening of the Pd in the allo y (again this mirrors the effect in PdPt although if the effect in PdNi and PdPt were the same then the PDOS should reveal opposing behavior). In this case, we attribute the observed behavior to domination by geometric (strain) effects. Ni in a PdNi alloy is effectively in expansion since the lattice constant of PdNi (3.76 Å) is larger than for plain Ni (3.52 Å). This results in the observed narrowing of Ni PDOS. Conversely, Pd is effectively in compression (lattice constant for Pd is 3.89 Å) and its d-band is expanded. Unlike the case for PdPt alloy, PdNi is dominated by strain effects and results in altering the reactivity such that Ni which is more reactive of the two metals becomes even more reactive upon alloying, and Pd the less reactive of the two metals, becomes even less reactive upon alloying. We have attempted to extend the trends for alloying of Pd with 3d metals which all possess a filled d-band (Zn, Ga and Ge). We have found that the d-band center is -2.62, -3.08 and -2.73 eV for PdZn, PdGe and PdGa, respectively. Therefore, there is an increase in d-band center relative to the Fermi level in all three cases compared to plain Pd bulk (-2.01 eV). Further observation of the simulated Pd PDOS shows a substantial depletion of d-states at the Fermi level and a contraction of the d-states for all three alloys. In addition, this trend is confirmed if we look at the Bader charge analysis of the system. The amount of charge transferred from Pd to Ga, Zn and Ge is -0.47, -0.41 and -0.29 e- respectively, showing that the magnitude correlates with the observed trend in the position of the leading edge. Furthermore, the work functions for Ga, Zn and Ge are 4.2, 4.33 and 5.0 eV, respectively. It shows that the trend correlates with the work function of the alloying el ement. Second, we have examined acrolein hydrogenation as a test reaction for an examination of alloy effects in support of experimental work with Chris Marshall and Jeff Miller in CSE. Acrolein hydrogenation can proceed via two paths as either the aldehyde functionality (forming propanal) or the double bond (forming allyl alcohol) may be hydrogenated. Furthermore there are two intermediates along each path as the first hydrogen is added in a different location than the second location (hydroxyallyl, allyloxy, 1-formylethyl and 2-formylethyl). We have examined the full reaction pathway on Ag(111) (the thermodynamically preferred surface of Ag) and compared Ag with AgIn alloy surfaces as AgIn alloys have been shown to exhibit superior selectivity for allyl alcohol. First, we find that the rate limiting step over all surfaces may not be hydrogenation of acrolein or any intermediate but rather hydrogen activation as hydrogen dissociation has a barrier exceeding 1.3 eV on all surfaces. Second, acrolein bonds very weakly to Ag surfaces and can adopt essentially any orientation. Focusing on the differences between the paths on the Ag(111) surface it can be assumed that the most favourable reaction path towards allyl alcohol is that of allyloxy as intermediate and that production of propanal follows the 1-formylethyl path. Comparing the first step of the reaction from adsorption of acrolein to the intermediate, it is clear that the presence of indium in the catalyst in the case of allyloxy does not make a big difference in the activation barrier or the reaction enthalpy. On the other hand, the barrier for hydrogenation of acrolein to 1-Formylethyl greatly increases with increasing In content. Overall the results suggest that the activity of the In containing catalysts should decrease while the selectivity increases. Calculations will continue on two fronts. First, we will continue our analysis of XANES data of alloys with CASTEP. We will now shift our focus to core-shell alloys. In collaboration with Mike Wong from Rice University, we have examined the XANES of PdAu core-shell alloys (Pd is the shell) with varying ratios of the two metals. We are now in the process of building appropriate models to explain the experimental results with the hope that we can develop general rules which can predict the XANES spectra (and reactivity) for any combination of core-shell alloys. Second, we will continue to examine acrolein hydrogenation over Ag surfaces but our focus will now move to dilute alloys using the VASP code. Recently our experiments have shown that the reactivity of Ag0.999X0.001 alloys can be significantly higher than Ag alone and can possess higher selectivity as well. We will examine unit cells with a single surface atom of Pd (or Ru, Rh etc.) as a model for these dilute alloy systems. The working hypothesis is that isolated metal atoms may help activate hydrogen (or act as anchoring points for the C=O bond in acrolein). We will perform calculations on these systems to test how non-contiguous atoms may aid in improving the catalysis. Finally we will begin our examination of neopentane hydrogenolysis/isomerization to support additional experiments in Jeff Miller’s lab. Hydrogenolysis involves a carbon cleavage and hydrogenation and results in butane and methane.Isomerization involves a ring closure-ring opening through a cyclopropyl intermediate to produce iso-pentane. The primary products would be methane and i-butane for hydrogenolysis and iso-pentane for isomerization. In both cases, further reaction steps can occur to produce secondary products, such as propane and additional methane. Isomerization of the primary product, iso-pentane, can lead to formation of n-pentane. Our preliminary experiments indicate that while Pd has a preference for the hydrogenolysis pathway (5% selectivity to n-pentane), Pt produces both n-pentane and isopentane (combined 60% selectivity). In addition, there are both size and alloy effects for this system. We will focus on understanding the reaction pathway for both hydro genolysis and isomerization on Pt(111) and Pd(111) in an effort to understand the selectivity differences. If successful, we will move to examine PdPt alloys which are even more selective than Pt surfaces. Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 450000 Q1: 100000 Q2: 100000 Q3: 100000 Q4: 150000 Justification: Thank You, The LCRC Accounts System

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New LCRC report submitted for Multicomp_Nanopart
by support＠lcrc.anl.gov 28 Aug '12

28 Aug '12

Full project report at https://accounts.lcrc.anl.gov/reporting/project/2012/?project=Multicomp_Nan…

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