Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Fanjie Kong Project Name: Comp_POP_Catalysts Division: CSE Project title: Computational studies of copper metalated catechol-containing porous organic polymers catalysts Associated funding: Catalysts Other Systems: None Science: The goal of this project is to explore, understand, and characterize, through modeling and simulations, the complex correlations between the structure, electronic features, and chemical reactivity of porous organic polymers (POPs) decorated with high densities of copper-(catecholate) groups. These discrete, monocatecholated complexes would be highly useful for applications such as gas storage,catalysis, or gas separations owing to their high specific surface area, good chemical stability and high structure control during synthesis. The central aim is to aid the ongoing experimental effort currently underway at CSE on synthesis of novel heterogeneous – primarily copper metalated catechol-containing POPs with superior activity and selectivity. Among the targeted catalytic transformations is selective oxidation of benzyl alcohol to benzaldehyde, which is a process of importance in various chemical technologies including those relevant to novel sources of energy. Project description: The planned computations will explore the structural, energetic, electronic, and catalytic functionality of two Cu centers in close proximity supported on catechol porous organic polymers (catPOPs). Our studies will study the connection of morphology, electronic features and catalytic functionality of two Cu centers catPOPs. The candidates for catalytic transformations (these systems will be tested) are the selective oxidation of benzyl alcohol to benzaldehyde. The activity and selectivity in the oxidation reaction of benzyl alcohol will be explored. The choices for the catechol-containing POPs and catalytic transformations are made based on the planned experimental investigations, some of which are currently undergoing. Within the planned studies, the issues that will be addressed are: 1) The atomic and electronic structures of a series of multinuclear aryl complexes of Cu(I) [Cun(Mes)n] will be explored. In solution they exhibit dimeric oligomers as the prevailing structure. In constrast, their solid state structures in crystals obtained from toluene solution show higer nuclearities such as [Cu(Mes)]5 which slowly turns toward the corresponding dimer in the respective solvent as observed by NMR in solution (the conversion of the pentamer to dimer). These stable homoleptic macrocycles exhibits quite symmetric arrays which can be roughly considered as D5h. The addtion of catPOP to the toluene solution resulted in the formation of CuI2catPOP(MesH) with the protolysis and elimination of MesH. What is the atomic arangement of the dimeric Cu(I) complex [Cu(Mes)]2 and the mechanism of the reaction for the formation of CuI2catPOP(MesH)? 2) The possible mechanism for the synthesis of catechol containing POPs CuIIcatPOP using a cobalt-catalyzed acetylene trimerization strategy will be addressed. 3) Use selective aerobic oxidation of benzyl alcohol to benzaldehyde to probe the catalytic activity and selectivity of CuI2catPOP(MesH).The benzyl alcohol can be oxidized selectively to the corresponding benzaldehyde at room temperature (25 ゜C) with air in acetonitrile solvent using a CuI2catPOP(MesH) and TEMPO as cocatalysts. The aim of the calculations will reveal the mechanism in the following respects as for the CuI2catPOP(MesH) catalyst: 1. What are the roles of TEMPO and CuI2catPOP(MesH) in the chemical transformation? 2. Why is this catalytic system so selective? 3 . What is the effect of the solvent(CH2CN) and ligand (“backbone”) on the reactivity? 4. What is the effect of the oxidation state of Cu on the reactivity? 4) Use propylene/propane as mixture to probe the selectivities of the single copper catPOP, the molecular packing as well as the shape and size of the pores in the amorphous single copper catPOP will be analyzed.The structural model of catpop framework materials has not yet been conclusively determined, there are few computational approaches to underpin the molecular design of amorphous porous solids, despite their possible practical advantages. For example, amorphous porous polymers can form robust, solution-processable separation membranes. A computational methodology for modeling the solid-state,amorphous packing of porous organic cages will be used to analyze void connectivity and simulate the diffusion of gases within the pore structure of the single copper catPOP. 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 VASP, NWChem, CP2k 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 chemical properties for two Cu centers catPOPs, and 2) the selective oxidation of benzyl alcohol to benzaldehyde is a priority research program which suits well with the high-performance infrastructure of the computational resources. Industry partnership: Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 640000 Q1: 160000 Q2: 160000 Q3: 160000 Q4: 160000 Justification: The scaling efficiency is indicated by the following example for NWChem as evaluated by us for One Cu catechol POP system (total of 962 basis functions): Cores Average SCF cycle (s) 96 1500 120 1000 Storage requirements: Thank You, The LCRC Accounts System