Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Sanjubala Sahoo Project Name: Multicomp_Nanopart Division: CSE Project title: Next Generation of Multicomponent Nanocatalysts: Computational Studies Associated funding: Strategic Initiative on Material for Energy (LDRD 2012-123-R1) Other Systems: None Science: The goal of this project is to explore, understand, and characterize, through modeling and simulations, the complex correlations between the size, composition, structure, thermal properties, electronic features, and chemical reactivity of multicomponent nanoparticles. The central aim is to aid the ongoing experimental effort currently underway at CNM and CSE on synthesis of novel heterogeneous - primarily binary and ternary metallic - nanocatalysts with superior activity and selectivity. Among the targeted catalytic transformations are selective hydrogenation of unsaturated hydrocarbons and aldehydes, which are the processes of importance in various chemical technologies including those relevant to novel sources of energy. Project description: Our aim is to study the structural, energetic, electronic, and catalytic activity and selectivity of elemental and multi-component transition metal nanoparticles both in gas phase and supported on substrates. Among the targeted nanocatalysts are Pt with deposits of Co, Ni, Fe, and Pd cations (the work on has been initiated already). Our studies have been extended to semi-infinite slabs of different transition metals such as Pt, CoPt3, FePt, FePt3 and others. The candidates for catalytic transformations (these systems will be tested) are the selective hydrogenation of unsaturated aldehydes such as citral with and without the vicinity of modifying ligands such as metal cations and primary alkylamines where the modifiers can be used to tune the catalytic activity and selectivity of the nanocatalyst for citral hydrogenation reaction. The experimental investigations with respect to the catalytic functionality of nanocatalysts are currently undergoing. We will be dealing with the following issues within the planned studies. 1) Use of size, structure and composition of the nanocatalysts as "knobs" for tuning their activity and selectivity for the hydrogenation of unsaturated aldehydes. In this respect, computations have been performed for finite size systems (55-atom elemental and binary cuboctahedral clusters). These studies have been extended to (001) and (111) surfaces of bulk crystal. 2) To study the effect of modifiers on the catalytic functionality of transition metal nanocatalysts, Fe dopants have been used where the effects of increased concentrations of both neutral and charged Fe dopants will be studied on the catalytic functionality of Pt nanocatalysts. Already some calculations have been performed in this direction where the energetics for different adsorption conformations have been studied as a function of concentration and location of Fe dopants with a preadsorbed citral on Pt55 cuboctahedron. We also plan to study the effect of alkylamine on the catalytic functionalty of Pt nanocatalysts, where we will be dealing with the adsorption energetics of amines as well as its concentration. The calculations in this regard have been partly performed. In addition, we will also be addressing the issue related to the simulataneous adsorption of Pt55 nanocatalyst by Fe and amines on the selective hydrogenation of citral. 3) To use the Infrared (IR) spectra as a tool to identify the actual adsorption conformation of citral on pure and modifier covered Pt nannocatalysts as observed in measurements. We have obtained a good agreement between the computed and the measured spectra for gas-phase as well as the supported citral. The computational studies of the structural, energetic, and electronic structure aspects will be performed using density functional theory. The packages that will be utilized include NWChem (uses plane wave and localized basis sets), VASP (uses plane wave basis sets) and Crystal. Naturally, we will benefit from the efficient scaling of the codes and take advantage of it in order to explore systems with still increasing number of atoms. Thus in our project: 1) The study of the properties of the nanocatalysts for different size of nanoclusters, ranging from a few tens to a few hundreds of atoms, and 2) the effect of different surfaces and composition of the supporting substrates is a priority research program which suits well with the high-performance infrastructure of the Fusion computational resources. Industry partnership: Project URL: http://blogs.anl.gov/major_initiatives/materials-for-energy/ Current FY Hours Used: undetermined amount New FY Requested allocation: 320000 Q1: 80000 Q2: 80000 Q3: 80000 Q4: 80000 Justification: The CPU-hours requested is based on the estimates made with NWChem and VASP on Fusion. It shows that NWChem scales well over large number of processors as listed below in comparision to VASP. The test for citral adsorbed on Pt55 cluster with total number of atoms N = 82 has been performed with 32, 64,128 and 256 processors show a substantial increase in performance with the increase in the number of processors up to about 128 processors for NWChem. Scalability of NWChem and VASP on Fusion for supported citral on Pt55 cluster consisting of 82 atoms: Cores Average SCF cycle (s) ---------------------------------------- NWChem VASP ----------------------------------------- 32 9607.47 32.34 64 4839.63 17.27 128 2479.27 11.66 256 1853.55 7.28 Storage requirements: Thank You, The LCRC Accounts System