Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Ujjal Das Project Name: 1atomCat Division: MSD Project title: Supported Single-atom Catalysts for Activation of Small Molecules, including Alkanes Associated funding: BES Chemical Sciences Other Systems: NA Science: Supported single-atom catalysts show exceptionally high catalytic activity compared to metal surfaces and sub-nanometer metal clusters. This high activity is attributed to large surface area of an isolated atom as well as its low coordination number. Standard techniques have been devised to prepare thermally stable single-atom catalysts using atomic layer deposition (ALD). In brief, supported single-atom catalysts show potential to activate very difficult bonds, including the ones in alkanes, with very high turn-over frequency. However, very little is known about the background working principles of such single-atom catalysts. For example, how the nature of bonding of the single-atom affects its catalytic activity, how local charge density varies for different single-atom types, the role of a support, and an atomic level understanding of the mechanism of activation of small molecules. All these information are useful to control the activity and selectivity of the c atalyst as well as to establish a structure-function relationship to understand the way such catalysts work. We plan to obtain all these information using high-level quantum chemical calculations for silica supported single-transition-metal catalysts. Project description: 1. The computational methods and programming models remain same from our previous submission and have been described below: Density functional theory (DFT) calculations will be performed to determine structure, bonding, and reaction energies of supported single-atom catalysts. Periodic boundary condition (PBC) will be imposed in order to maintain periodicity of the solid support. B3LYP hybrid functionals will be used in general, however, we may also switch to gradient corrected density functionals (GGA), where, B3LYP is either very expensive or not applicable. The Nudged Elastic Band (NEB) method of Henkelman and coworkers will be used to calculate transition states and activation barriers. Surface phonons will be calculated for accurate estimation of reaction free energies. Bader charge analysis and NBO population analysis will be performed to obtain information about local charge density and orbital electron density of the single-atom catalyst. 2. Software requirement mostly remains same. We request one additional program (Lammps): (a) VASP 5.0 or later (b) Gaussian-09 (c) Matlab (d) Lammps Additional Comments: We have problems running parallel VASP-5.2.11 on Fusion. This has been notified to LCRC support staff. We request updates from them on this issue. 3. Performance achieved: We have made significant progress since the allocations were made on June, 2012. We have developed accurate cluster models representing amorphous silica surface. Using these models, we have successfully identified the defect sites on dehydroxylated silica. The defect sites mostly contain strained three- and four-membered rings of Si-O bonds. Our calculated surface Raman spectra of the defect sites match well with the experimental results obtained by our collaborators. Using the cluster models, we have also identified the binding sites for metals on the silica surface. In general, the metals prefer to bind at the defect sites forming metal-O bonds. The binding process is highly exothermic as it leads to the opening of the strained rings. So far, we have completed structure evaluations for iron (FeIII) and zinc (ZnII). Future studies will focus on Ni, Co, and Cu. For iron, we have calculated different vibrational modes of silica adsorbed Fe(III) atom and found that only the sym metric Fe-O stretching modes, in different combinations, appear in the experimentally observed UV-resonace Raman spectra. This is a new and exciting observation and will be published soon. 4. Future Research: In the FY-2013, we will mainly study catalytic activity of different silica supported single-atoms. We will begin with hydrogenation and dehydrogenation of propylene by Zn. First, we will identify all the intermediates in the catalytic cycle. Their thermodynamic stability will be assessed from the heat of formation energy. Activation barriers will be computed to see if the formations of these species are kinetically feasible. We will also verify if the intermediates play any role in poisoning the catalyst. CO oxidation is another important reaction often used to study catalytic activity. We will identify the CO binding sites on Zn and develop a complete mechanism of CO oxidation to CO2. The role of the support in this process will be investigated in details. CO oxidation and hydrogenation will be studied for Fe(III) also. In summary, FY-2013 resources will be used mainly for the following research activities: 1. Zn as a catalyst (hydrogenation/CO oxidation) 2. Fe as a catalyst (hydrogenation/CO oxidation) 3. Identify structures of Ni/Co/Cu on silica 4. Identify the role of support on catalysis 5. Requests and justifications: Energy optimization using VASP takes approximately 1000 CPU hours. Hessian (second order energy derivative) evaluation takes roughly 1500 CPU hours. Optimization and Hessian evaluation using Gaussian take approximately the same time for model clusters, 150 CPU hrs. For each quarter, we estimate to run 50 geometry optimizations and 25 Hessian calculations using VASP, and 200 Gaussian calculations, a total of 117500 CPU hrs. Therefore, our total request for FY-2013 is 470000 CPU hrs. The PI of the project is Dr. Ujjal Das. Dr. Larry Curtiss, a Distinguished Fellow at the Argonne National Lab, is a co-PI and the contact person for this project ([email protected]). We will notify if a new member joins this project or if additional resources are required. Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 470000 Q1: 117500 Q2: 117500 Q3: 117500 Q4: 117500 Justification: Thank You, The LCRC Accounts System