Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Juan Lopez-Encarnacion Project Name: Comp_Soft_Catalysts Division: CSE Project title: Soft Catalysts for Green Chemistry and Energy applications Associated funding: Strategic Initiative on Materials for Energy (LDRD-2012-060-R1) Other Systems: None Science: The objective of this project is to perform extensive modeling and computational studies that will aid in design and synthesis of new catalytic materials for efficient transformation of abundant C1 sources (carbon dioxide (CO2) and methane (CH4), in particular) into chemical feedstocks and fuels. The planned theoretical/computational work will be performed in close contact with the ongoing experimental effort on the subject at CSE. The goal is to design and synthesize a new type of catalytic materials that will combine the best characteristics of both homogeneous catalysts (high selectivity at low temperature, tunability) and heterogeneous catalysts (stability, ease of separation). Such catalytic systems are not available at present. Project description: In the FY2013, the computational studies will focus on thermal stability of crystalline and amorphous porous organic polymers (POPs) with and without the reaction centers incorporated into it. The dynamics/kinetics and elucidation of the paradigmatic reaction mechanism of the catalytic chemical reactions that will be explored experimentally. Specifically, we will explore the alkane metathesis reaction mechanisms promoted by Ta-based/POP catalysts. One of the targeted processes is conversion of ethane into methane and propane. Based on our preliminary results, we expect the Ta-based reaction centers embedded on POP supports to reduce the relevant reaction barriers as compared to those of the more common supports, e.g., silica or alumina based. The structural and electronic aspects of reactants, intermediates, transition states, and products will be explored and characterized using state-of-the-art density functional theory. In addition, we are planning the development, implementation, and use of new methodologies for generation of 3D amorphous structures for POPs from nodes and/or struts, i.e., building blocks of the POPs, with multiple “heads” and “tails” (the current methodology allows for only one head and tail per node/strut, limiting the generation of POPs to one chain or 1D). Here, the static and random modeling of incorporation of reaction centers into amorphous POPs will be studied as well. The number of atoms treated at a time will vary from a few to a few tens (e.g., in organometallic reaction centers), from tens to about a hundred (e.g., in struts), and to a few hundreds (e.g., in POP networks). The bulk of the planned computations will be performed with the SIESTA code, which is an efficient order-N density functional theory (DFT) algorithm (i.e., the computational time scales linearly with the size of the system). In the case of generated 3D amorphous POP networks, the studies in will require inclusion of thousands of atoms, and they will be performed using efficient and at the same time adequate semiempirical potentials and/or force fields to characterize their low-energy structures and dynamical aspects. Then single-point DFT treatments will be performed on these structures to characterize their electronic features using SIESTA or CP2K which allow to performed calculations for thousands of atoms. The dynamical and thermal behavior will be explored using both first principles based and semiempirical potentials/force fields. The kinetic aspects will be evaluated and characterized using transition state theory. In addition to the SIESTA and CP2K codes we will also use other packages (e.g., LAMMPS, NWChem, and Gaussian) as appropriate. The requested time is based on estimates performed on Fusion (see below). The methods used to study the dynamical/kinetics aspects of our systems require considerably computational power/time than those methods used during the FY2012 and the test show below (e.g., crystal, atomic, and electronic structure computations). The expected number of project members is three (3) or more. Project URL: http://www.cse.anl.gov/catalysis_energy_conversion/homogeneous/index.html Current FY Hours Used: undetermined amount New FY Requested allocation: 980000 Q1: 245000 Q2: 245000 Q3: 245000 Q4: 245000 Justification: The scaling efficiency on Fusion was tested using the code SIESTA in the full optimization of the atomic structure and cell volume of a crystalline porous organic polymer, which contain a total of 584 atoms: 192 atoms of H (5 numerical basis function per each H), 360 atoms of C (13 numerical basis function per each C), and 32 atoms of O (13 numerical basis function per each O) in its unit cell; a total of 6,056 basis functions. Substantial speed-up is achieved with the increase in the number of cores: Cores Average elapsed time per optimization step (min) 16 4.38 32 2.70 64 2.34 128 1.68 Thank You, The LCRC Accounts System