August 2016 - Allocations-admins - mailman3.cels.anl.gov

New LCRC report submitted for cdft
by support＠lcrc.anl.gov 26 Aug '16

26 Aug '16

Full project report at https://accounts.lcrc.anl.gov/reporting/project/2016/?project=cdft

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[LCRC Accounts] Yearly Allocation Request for Bio_catalysis
by accounts＠lcrc.anl.gov 24 Aug '16

24 Aug '16

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Cong Liu Project Name: Bio_catalysis Division: MSD Project title: Biomass Catalysis for Energy Associated funding: Director's Fellowship at Argonne Other Systems: Science: A critical challenge for biomass conversion to fuels is to develop efficient multi-functional catalysts that facilitate the complex multi-step processes. The necessary chemical conversions in biomass catalysis often include ring opening (e.g., C-O bond breaking), dehydroxygenation/hydrogenation, and coupling reactions, etc. It is known that most of the metal-containing catalysts are only able to catalyze one specific conversion step effectively, while possibly failing on other steps. This is due to the different reaction mechanisms involved in different chemical conversions. For instance, our previous studies of CO2 activation by 3d transition metal complexes have shown that C-O bond cleavage occurs more easily with earlier metal catalysts while hydrogenation reaction favors with later metal systems. On the other hand, current multi-functional catalysts show lack of efficiency and often require high temperature and pressure. Better understanding the reaction mechani sms of biomass conversions using computational tools is essentially crucial to new catalysts development. Our group has considerable experience in the area of computational modeling of catalytic pathways as well as molecular simulations on accurately predicting thermochemical properties of chemical conversions of sugar molecules. These studies show, among other findings, that reaction mechanisms of biomass catalysis can provide valuable insights and guidance for experimental discovery of novel catalysts. Our work in this area will be using first principle-based calculations to develop better understandings of the possible reaction pathways for conversion of biomass-derived molecules. Anhydrosugars and furans are major primary products from biomass pyrolysis. These C5 or C6 compounds are potential source to synthesize diesel fuels that are a mixture of C8-C21 hydrocarbon compounds. In order to convert the C5 or C6 chemicals into diesel fuels, an important step is to activate a C=C bond to carry out C-C coupling reaction. On the other hand, ring opening and hydrogenation will be used to either saturate a C=C bond or to remove the oxygens. Recently, nano-scale materials have received increased attention on biomass catalysis, because of the ability of these materials to activation inert chemical bonds. For instance, Atesin et al has reported a selective etheric C-O bond hydrogenolysis catalyzed by Ln(Otf)3/Pd-nanoparticles in ionic liquid. Therefore, designing appropriate nano-sc ale heterogeneous catalysts that can facilitate C-C coupling reaction, and multi-functional catalysts for both ring-opening and hydrogenation, is a key scientific challenge that we are going to address in this project. In the next stage of this project, our studies will be focused on development of effective solid-state catalysts for the functionalization of alkenes and alkanes, e.g., selective hydrogenation and dehydrogenation reactions. The considered catalysts include, polymer or metal oxide supported single-site transition metal catalysts and metal and intermetallic nanoparticles. Project description: Quantum mechanical calculations will be carried out as follows: a. Reaction pathways The themochemistry of individual reactions with detailed reaction pathways including important intermediates and transition states is the essential first step towards the understanding of the chemical transformations. This will be investigated using the suitable computational method from step a. Since the chemical transformations such as hydrogenation reactions are rather complicated and will generate many possible intermediate and product species, detailed reaction pathways and all the possible species will be calculated. c. Development of effective catalysts for hydrogenation/dehydrogenation reactions The hydrogenation reaction is the key step to convert biomass-derived oxygen-rich compounds or alkenes to fuels. The future computational studies will not only help understand the reaction mechanisms of these reactions, but also predict effective solid-state catalysts for these reactions prior to experiment. Single-site metal catalysts have well-defined structures and catalytic properties, thus the activity descriptors of these catalysts will be established based on both computational and experimental studies, and novel effective catalysts will be predicted based on the developed activity descriptors. d. Multi-functional catalysts for ring opening and hydrogenation reaction An important step of getting the diesel fuel products is to remove the unsaturated bonds and oxygens in the longer chain carbon compounds. In many cases, this step involves both ring opening (breaking C-O bond in a ring) and hydrogenation (removing oxygens). To facilitate both reactions, efficient multi-function catalysts need to be developed. An ideal catalyst would be a bimetallic nanoparticle catalyst supported on a high surface area material, in which one metal acts as an oxophilic acid to reduce the polar bond and the other metal is being a base to help produce dissociated hydrogen. Potential catalysts include intermetallic nanoparticles, as well as metal nanoparticles-zeolite catalysts. The catalytic properties will be measured by reaction energetics. The calculations of this project will include both molecular (Gaussian) and periodic calculations (VASP). For Gaussian calculations, each calculation will take 1 processor for approximately 20-40 hours. For VASP calculations, each calculation will take 64 processors for about 20 hours. Approximately 800 gaussian calculations and 300 VASP calculations are required. Thus totally about 420000 cpu hours are necessary. Industry partnership: Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 420000 Q1: 105000 Q2: 105000 Q3: 105000 Q4: 105000 Justification: Storage requirements: Thank You, The LCRC Accounts System

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[LCRC Accounts] Yearly Allocation Request for Solar_EPR
by accounts＠lcrc.anl.gov 24 Aug '16

24 Aug '16

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Jens Niklas Project Name: Solar_EPR Division: CSE Project title: Solar energy conversion in organic photovoltaics Associated funding: DOE Division of Chemical Sciences, Geosciences, and Biosciences Other Systems: Dr. Mardis has three small linux clusters (12/24/48 nodes) which are housed at her home institution. Her research group is the sole users of these systems. Orca, pqs, gabedit, and gamess all can be run on these systems. Science: This work is focused on elucidating the electronic structures of electron donor and electron acceptor molecules which are the most promising solar conversion material for organic photovoltaic devices. A key process of the solar energy conversion in organic photovoltaics is the initial charge separation. Delocalization of the positive and negative polarons on the molecule minimizes wasteful charge recombination. The delocalization correlates with solar energy conversion efficiency and is determined by the electronic structures of the organic molecules. The first aim is to use Density Functional Theory (DFT) to evaluate the extent of polaron delocalization on these systems. The second aim is to explore the effect of solvent and conformation on the calculated magnetic resonance parameters in order to assess the feasibility of this approach for modeling the bulk systems. These results will facilitate interpretation of our multifrequency Electron Paramagnetic Resonance (EPR) data of polymer fullerene bulk heterojunction (BHJ) solar cells. This study will provide a rationale for design of efficient BHJ blends. Project description: We are evaluating the effect of modifying the electron donor part of BHJ solar cells to modify the delocalization of positive polaron, which correlates with solar energy conversion efficiency. Prior work studied delocalization in polymers, oligomers, and monomers of various molecular systems. We will extend our studies to new molecules of interest, which have been reported to provide high efficiencies in organic photovoltaic. This includes the study of electron donor molecules used in small molecule BHJ solar cells which was started in the end of the last FY. In addition, novel non-fullerene based electron acceptors have been recently reported and our collaborators are synthetizing these acceptors for us. DFT calculations will be performed to determine their electronic structure and magnetic resonance parameters. These results will then be compared with our experimental results on BHJ solar cells containing these novel acceptors. We intend to run a series of gas-phase model DFT optimizations to determine the low energy conformations of the various using standard ab initio optimization codes such as Gaussian09, GAMESS, or NWCHEM. This will also allow us to generate a set of conformers likely to be present in the experimental samples. The resultant conformations will be used to calculate EPR parameters (g-tensors and hyperfine coupling constants) using Orca 3.0.3. The initial structure building, monomer and dimer test calculations, and analysis of spin densities will be carried out on our lab computers. The optimization subroutines of NWCHEM, Gaussian09, and GAMESS are highly parallelized. Orca 3.0.3 is a highly accurate program for calculating EPR parameters. Benchmarks on fusion with Orca showed good scaling up to 16 processors for the EPR parameter subroutines. Prior optimization calculations on fusion for the largest oligomer we have calculated so far took about 250 (B3LYP; small basis set) to 425 (Long range functional; medium basis set) CPU hours for optimization. Frequency calculations required the bigmem queues and approximately 5000 CPU hours. The EPR parameter calculations (g-tensor) took 50-150 CPU hours with the largest oligomer requiring the bigmem queue. We anticipate also calculating the hyperfine coupling constants which in test calculations added about three times the computational cost per molecule so each EPR calculation will require 200-600 CPU hours with the longer ones requiring the bigmem queue. Thus, assuming three functionals for each of 10 oligom ers with 4-8 conformations for each requires 66,000 CPU hours for optimization with an additional (5000 CPU x 10 conformations x 3 functionals x 2 bigmem cost)300,000 CPU hours for frequency calculations on the lowest energy conformation for each molecule and functional. The EPR parameter (hyperfine and g-tensor) calculations will take 50,000 (an estimate with some on bigmem) CPU hours. This totals to 416,000 CPU hours. Since we anticipate some of the frequency calculations being possible on other computer systems, and some speed-up with the transition from fusion to blues, we are asking for slightly less (360,000 CPU hours). This is in good agreement with our prior usage of approximately 30K CPU hours/month over the past few months as we’ve moved from benchmarking and testing to production runs. Industry partnership: Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 360000 Q1: 90000 Q2: 90000 Q3: 90000 Q4: 90000 Justification: Storage requirements: 1TB Thank You, The LCRC Accounts System

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[LCRC Accounts] Yearly Allocation Request for Hetero_Catalysis
by accounts＠lcrc.anl.gov 24 Aug '16

24 Aug '16

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Cong Liu Project Name: Hetero_Catalysis Division: CSE Project title: Development of Novel Heterogeneous Catalysts for Effective CO2 Conversion to Fuels Associated funding: Catalysis group fundings Other Systems: Science: The conversion of CO2 to fuels is of use for renewables in carbon-neutral technologies and for developing approaches to mitigate global warming. The high thermodynamic stability of the CO2 molecule requires substantial input of energy for its reduction and conversion. Although a number of recent studies have helped to better understand CO2 activation/reduction using catalysts, the catalytic conversion of CO2 to hydrocarbon fuels (e.g., CH3OH, CH4) is still a challenging problem. For instance, although CO2 has been shown to be reduced directly on metal surfaces, the surfaces become quickly poisoned and deactivated by the reduction products (e.g., CO).[1] Studies have achieved the reduction of CO2 to CO and formate. However, further transformation of CO and formate to more useful products such as methane or methanol requires multiple hydrogenation steps, and has only been demonstrated with low efficiency. Our work in this area will be focused on using computational methods to understand the chemical insights of the reductive conversion of CO2 to hydrocarbons on supported transition metal nanomaterials. Materials including subnanometer metal clusters and 2-dimensional transition metal dichalcogenide (TMDC) nanoflakes are taken into account. The computational studies provided not only the molecular understanding and explanations for the experimental results, but also predicted critical trends of the catalytic properties of different materials, where were confirmed by the experimental studies. Project description: Previously, we have developed highly active supported Cu4 for CO2 hydrogenation to Ch3OH at low pressures (J. Am. Chem. Soc., 2015, 137 (27), 8676), as well as highly active electrocatalyst, WSe2, for the electrochemical reduction of CO2 to CO (Science. 2016, 353(6298), 467.) In the following year, we are going to focus on detailed studies of the catalytic properties of transition metal dichalcogenide nanoflakes for electrochemical CO2 reduction: 1. Modifications of the TMDC materials and their catalytic properties. Metal ion doped MoS2 and WSe2 nanoflakes are of great interest. The structural changes, electronic effects and electron transfer properties will be studied using periodic density functional theory calculations. The catalytic properties for CO2 reduction of these doped TMDC materials will be compared will the pure TMDC materials. 2. Electrochemical reduction of CO2 to hydrocarbons on TMDC nanoflakes. Previously, the computational and experimental efforts were only focused on CO2 reduction to CO. In our experimental device, the products are a mixture of CO and H2 (syn-gas), which can be used for the synthesis of hydrocarbon fuels. It would be a significant improvement of the catalytic system if CO2 can be converted directly to hydrocarbon fuels. Future computational studies will be focused on understanding the electrochemical reduction of CO2 to hydrocarbon fuels on TMDC nanomaterials, and predict effective catalytic systems prior to experiment. Reaction mechanisms and energetics will be investigated systematically for a series of TMDC materials, and the most promising catalyst system will be identified for further experimental studies. 3. The role of ionic liquids in the electrocatalysis of CO2 reduction. In our previous studies, we discovered that utilizing ionic liquids in the electrolyte system promotes the catalytic performance of the TMDC nanomaterials for CO2 reduction. However, the exact role of the ionic liquid is still unknown. In the future studies, we are going to carry out detailed computational studies to investigate the interactions between ionic liquid ions and the electrode (catalyst) active site, and the electronic effects of the ionic liquid in the electocatalytic process. Both explicit and inexplicit solvent effects will be taken into account, and the effect of external potential will be studied. A regular calculation will require 64 processors of about 10 hours of running time. Approximately 700 calculations will be carried out, and totally about 450000 cpu hours will be necessary. Industry partnership: Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 480000 Q1: 120000 Q2: 120000 Q3: 120000 Q4: 120000 Justification: Storage requirements: Thank You, The LCRC Accounts System

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New LCRC report submitted for Bio_catalysis
by support＠lcrc.anl.gov 24 Aug '16

24 Aug '16

Full project report at https://accounts.lcrc.anl.gov/reporting/project/2016/?project=Bio_catalysis

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New LCRC report submitted for Hetero_Catalysis
by support＠lcrc.anl.gov 24 Aug '16

24 Aug '16

Full project report at https://accounts.lcrc.anl.gov/reporting/project/2016/?project=Hetero_Cataly…

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[LCRC Accounts] Yearly Allocation Request for Atmos_Chem
by accounts＠lcrc.anl.gov 24 Aug '16

24 Aug '16

Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Rao Kotamarthi Project Name: Atmos_Chem Division: EVS Project title: Process Scale Modeling of Atmospheric Chemistry and Transport Associated funding: DOE,DoD Other Systems: NERSC Science: The scientific aim of the proposed modeling activity is to further the understanding of the chemistry and distribution of aerosols over certain regional domains and calculate the heating rates as a result of increased aerosol loading primarily over India. A second objective is to use Ensemble Adjusted Kalman Filter technique for data assimilation of satellite data sets into global chemical transport models to estimate model biases in calculating trace atmospheric gas constituents and aerosols A third objective is to perform dynamic downscaling of climate model simulation results for regional scale applications. In particular, we will focus on the uncertainties in downscaled projections resulting from boundary conditions, the utility of spectral nudging and grid scale nudging for improving the energy balance of regional scale climate models over long integration times. Project description: We continue to investigate the regional scale climate modeling and climate feedbacks from aerosols. The models employed for these studies include (a) WRF-CHEM (b) WRF (c) MPAS and (3) GEOS-CHEM. Each of these models has been ported to the Blues cluster to perform calculations by our group. All the codes use a mix of MPI and OpenMP programming models and can scale for as few as 4 nodes to several hundred. The WRF, MPAS and the WRF-CHEM models are highly scalable and limited by job turnover times and queue limitations. The project will have approximately 4 members. Industry partnership: Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 200000 Q1: 50000 Q2: 50000 Q3: 50000 Q4: 50000 Justification: The models we use are highly scalable (WRF, WRF-CHEM and MPAS). We have scaled these models to several thousand cores on ALCF and NERSC systems. We plan to use WRF model in LES mode for some of the calculations this year. Storage requirements: Thank You, The LCRC Accounts System

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New LCRC report submitted for Solar_EPR
by support＠lcrc.anl.gov 23 Aug '16

23 Aug '16

Full project report at https://accounts.lcrc.anl.gov/reporting/project/2016/?project=Solar_EPR

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New LCRC report submitted for LiBattModeling
by support＠lcrc.anl.gov 23 Aug '16

23 Aug '16

Full project report at https://accounts.lcrc.anl.gov/reporting/project/2016/?project=LiBattModeling

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[LCRC Accounts] Project Request: BrewerDefectsForm
by accounts＠lcrc.anl.gov 22 Aug '16

22 Aug '16

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: John J. Low Applicant's institution: ANL Applicant's division: Brewer Science Propriety Project Project Name: BrewerDefectsForm Project title: Brewer Science Defect Formation Project Associated funding: Brewer Science Other Systems: Science: Density functional theory and ab initio-based methods will be used to analyze the formation of defects in BSI materials. By modeling the polymerization reaction, we can determine the mechanisms leading to varying types of defects for a specified material and develop methods of predicting the formation of such defects. We will use GAMESS to investigate bonding along the reaction pathway and any mechanisms that could lead to side products. These results may be used to predict novel polymer materials and address customer requests for polymers with specific physical and chemical characteristics. Project description: First principles methods will be used to analyze the formation of defects in BSI materials. By modeling polymer bonding interactions and determining bond energies, we can determine the types of defects that may form in a specific material and the bonding interactions that are significant for the stability of the polymer. We will use GAMESS to investigate the bonding at these sites and any mechanisms that could lead to side products. The details of this project are further outlined in the Milestones as follows: M1: Model the polymer, systematically determine bond dissociation energies M2: Determine the reaction pathway for successful polymer synthesis and formation of possible side products M3: Model the reaction pathway for a proposed polymer M4: Simulate polymer for a novel material and predict defect behavior GAMESS will be used to conduct calculation of bond dissociation energies and molecular interactions. If successful, these results may be used to predict novel polymer materials and address customer requests for polymers with specific chemical characteristics. Industry partnership: This is a proprietary Brewer Science Project. Project URL: Requested allocation: 0 Q1: 0 Q2: 0 Q3: 0 Q4: 0 Justification: Storage requirements: 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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