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) Use of pyridine, acetonitrile, tetrahydrofuran and thioanisole as ligands for displacement of mesitylene for two Cu centers catPOPs. In this respect, computations have been partly performed for pyridine. The upcoming studies will be extended to acetonitrile, tetrahydrofuran and thioanisole as ligands. The maximum coordination number of ligands will be identified and the binding energies will also be calculated for them. A detailed NBO analysis of the charge transfer between the two Cu centers, the catPOPs backbones and the ligands will be presented. The relationship between the ligands displacement sequence and the charge transfer of the two Cu sites and the connection between the ligand exchange activity and the electronic structure (in particular the electronic configuration of the Cu atom) will be discussed. The mechanisms (dissociative, associative or interchange mechanisms) of ligands exchange and will be explored. 2) Use of oxygen molecule to probe the oxidation of two Cu centers catPOPs. Here we plan to explore the most preferred adsorption form (molecular adsorption or dissociative adsorption), the most preferred adsorption conformation and the reaction pathway. For this purpose some computations have been performed, where the potential energy surfaces are studied as a function of the distance between the mass center of the two oxygen atoms and the mass center of two copper atoms in the catechol-containing POPs. Another aspect of the work is the influence of the environmental factors, such as the presence of a solvent, on the morphology and/or the oxidation of two Cu centers catPOPs, in particular, in the involvement of acetonitrile, as a solvent in the catalytic transformations of oxidation of benzyl alcohol to benzaldehyde. 3) Use of benzyl alcohol for selective oxidation of benzyl alcohol. We will address the issue involving the mechanism of the selective oxidation of benzyl alcohol to benzaldehyde. A possible mechanism proposed by the experimentalists is the Stahl mechanism which consists of a two-stage catalytic mechanism (catalyst oxidation and substrate oxidation). Based on the Stahl catalytic mechanism, the reaction pathway of the selective oxidation of benzyl alcohol to benzaldehyde will be investigated. 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 Fusion computational resources. Industry partnership: Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 720000 Q1: 180000 Q2: 180000 Q3: 180000 Q4: 180000 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