Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Julius Jellinek Project Name: Comp_Nanocatalysis Division: CSE Project title: Theoretical/Computational Studies of the Fundamentals of One-Component and Alloy Metal Based Nanocatalysis Relevant to Alternative Sources of Energy Associated funding: EFRC/IACT funded by BES/DOE Other Systems: NERSC, ~650000 core-hours Science: The central objective of this project is to perform modeling and computational studies that aim at understanding and characterization of the chemical reactivity and catalytic functionality of pure and alloy metal nanoparticles at the microscopic (i.e., atomic and electronic) level. The systems and processes of interest are those defined in the project “Institute for Atom-Efficient Chemical Transformation”, a DOE Energy Frontier Research Center. The overall emphasis is on finding new ways of generating fuels from biomass. Specific examples of transformations of interest include reforming of glycerol and formic acid into H2. The goal of the planned computational studies is to aid the ongoing experimental investigations on synthesis of novel, primarily alloy, nanocatalysts and characterization of their various physico-chemical properties and catalytic characteristics. The aim is not only to explain the experimental findings but also to provide guidance to future ex periments. Project description: Taking use of by-products of biomass reforming, such as glycerol, as potential sources of hydrogen would further reduce our dependence on petroleum-based materials in production of fuels and other chemicals. Our computations in previous fiscal year were focused on the conformational and energetic characteristics of chemical transformations of glycerol and its derivatives on gas-phase pure Pt and mixed nanocatalysts. Through a comparison of energetics of competitive elementary reactions steps, especially reaction barriers, and the variations in these with catalyst composition, we succeeded to explain experimental observations indicating differences in catalytic activity and selectivity of bimetallic alloys. Our computations also have shown that energetically most facile routes for dehydrogenation, which is the desired reaction path in reforming, of glycerol and its derivatives include a series of proton transfers between hydroxyl branches of the reactant molecule. The overall reaction barrier depends on the availability of a route to transfer the energetically most suitable proton to the metal surface. When the reactant-metal nanoparticle system is in gas phase, these routes are products of the interaction between hydroxyl branches of the reactants and thus, strongly depend on the adsorption configuration of the reactant. When the system is in solution, as in the experiments are, interaction between water molecules and the reactant, specifically through hydrogen bonds, provide additional routes for transfer of proton and thus affect the catalytic activity. Additionally, they affect the preferred adsorption configuration of the reactant on the metal nanoparticle. For the next fiscal year, through a combination of static DFT and molecular dynamics (MD) based on forcefields, we aim to incorporate the solution effect into the modeling of reactivity of glycerol-metal nanoparticle systems. Configuration of water molecules around r eactant/metal nanoparticle will be explored with MD computations and through sampling the MD runs, we will obtain realistic models of the solution/nanocatalyst system. Dehydrogenation and other possible chemical transformation routes will be explored through DFT and combined QM/MM approach. We will take advantage of the high scaling efficiency of NWChem code to study the increased complexity of solution/metal interface modeling as compared to gas phase computations. Special emphasis will be put into the choice of exchange-correlation functional in DFT runs for an accurate definition of bonds between water and the reactant. Dispersion correction schemes as implemented in NWChem code will also be used. Project URL: http://www.anl.gov/catalysis-science/index.html Current FY Hours Used: undetermined amount New FY Requested allocation: 500000 Q1: 125000 Q2: 125000 Q3: 125000 Q4: 125000 Justification: The allocation request is based on previous DFT test runs with NWChem on Fusion and NERSC clusters. Scaling efficiency of parallel computations with NWChem is overall high. Tests for Pt12Mo-CO system (total of 554 basis functions) on Fusion using 32, 64, 128 and 256 processors show a substantial increase in performance with the increase in the number of processors up to about 64 processors. Cores Average SCF cycle (s) 64 9 128 6 Thank You, The LCRC Accounts System