Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: Rajeev Surendran Assary Project Name: Cat_Biomass Division: MSD Project title: Computational Studies of Biomass Catalysis Associated funding: BES, EERE Other Systems: CNM Argonne, Blue Gene/P Argonne, NERSC Science: This computational project will be performed to gain fundamental understanding of the chemistry of biomass reactions and help to design catalysts that improve the efficiency of biomass conversion to transportation fuels or industrial chemicals. The project is an integral part of the computational modeling and theoretic studies associated with the Argonne’s Energy Frontier Research Center (EFRC, IACT Argonne) and Computational Biomass Pyrolysis consortium funded by Energy Efficiency and Renewable Energy (EERE). Efficient chemical transformation of biomass is essential to produce sustainable energy and industrial chemicals. Conversion of biomass to useful chemicals include sequence of chemical transformation including, C-O bond cleavage and C-C/H bond formation. Main challenges facing the biomass conversion reactions are a plethora of undesired reactions and lack of efficient catalysts for various chemical reactions associated with biomass conversion process. Various reactions include dehydration, rehydration, isomerization, aldol/retro aldol reaction, ring opening/closing, carbon-carbon coupling, hydrogenation, and hydrodeoxygenation reactions. A detailed understanding of the chemistry of both desired and undesired reactions, together with the understanding of catalysis is essential for catalyst design for efficient biomass conversion. Project description: Catalytic C-O bond cleavage: Efficient catalytic cleavage of C-O bonds of biomass molecules is crucial to the conversion of biomass to transportation fuels and industrial chemicals. Recently, we have explored a series of lanthanide trivalent metal triflates as potential catalysts for the C-O bond cleavage in ionic liquids using combined quantum chemical methods. This theoretical finding is supported by the experimental studies. the metal triflate catalysts were found to be active for a series of ether substrates When used in tandem with hydrogenation catalysts (Pd/Alumina), etheric substrates afford industrially useful alcohols. In this proposal we would like to identify most efficient metal triflate catalysts for the conversion of ethers to alcohols and subsequently to alkanes using quantum chemical methods. This information regarding the catalysis can be then feed into experimentalists for testing. For computations, the density functional theory (DFT) will be used to compute various catalytic descript ors such as binding of ether substrates with the catalysts and the activation energy required to cleave the C-O bonds of various substrates. Calculations will also be performed to understand detailed reaction mechanisms to identify undesired reactions and to improve the efficacy of the catalyst by rational design. Various metal triflate catalysts with central metal atoms (Z=22 to Z=92) will be considered for this study. The oxidation states from +3 to +6 will be considered. Due to bulkiness and bidentate nature of the triflate ligands, upon coordination with highly positive metal ions (for example Nb (V) or Mo(VI)), it is likely that the first coordination layer of the central metal ion may be saturated by the triflate and the binding of ether-substrate and subsequent catalysis may be unlikely. Here, we propose to model such scenarios by mutating the ligands of M(OTf)n (n=4 to 6) by less bulky mono anionic systems ( for e.g. F-, CN- etc.) and compute the C-O bond breaking efficacy using DFT. Catalytic C-C coupling: Acidolysis or pyrolysis of biomass yields furans and Low Molecular Weight Carbohydrates (LMWC, contains C1 to C4 compounds). In order to convert these fragments to liquid transportation fuels, efficient C-C coupling is essential. To address the C-C coupling between the fragments two types of reactions are envisioned here, namely cyclo-addition reactions and aldol type condensations. The cyclo-addition reactions can be thermal or catalytic. First we will investigate detailed thermochemistry and activation barriers of likely cyclo-addition reactions between furan and LMWC (20-100 reactions) and rank these reactions based on thermodynamics and kinetics. Selected reactions will be further studied using various Lewis base catalysts to understand the catalysis and side reactions. These Lewis acid catalysts can be either metal ions or metal ions impregnated inside a porous cavity to provide a nano confinement for the catalytic process. These confinement effects will be modeled to un derstand their effects on catalytic reaction mechanisms. These calculations taking account of the effects of porous frame work can be computationally very demanding and we intend to perform combined Quantum Mechanical/Molecular Mechanical (QM/MM) simulations and subsequent periodic Carr-Parrinello Ab Initio Molecular Dynamics (CP-AIMD) simulations for the modeling of catalytic process. Second category of C-C coupling reactions that we would like to address is Aldol reaction combined with hydro cyclo addition reactions. The reaction sequence here is aldol reaction, hydrogenation in tandem with cyclo-addition reactions. In principle, these cascades of reactions can convert furans (C4-C6) to diesel fuels range chemicals (C14-C16). Two major challenges here are liquid phase hydrogenation of the aldol products and selectivity of hydrocycloaddition reactions. To address these challenges, first, we intend to understand the energy landscapes (including reaction barriers) of these reaction networks using accurate quantum chemical methods (G4 methods, CCSD(T)). Using this valuable information, we intend to perform dynamic simulations including the effects of explicit solvent molecules and various base catalysts (Lewis base) for aldol reactions. Similar calculations were indented to study liquid phase catalytic hydrogenation as well. in terms of softwares, we intend to use Gaussian 09 and CPMD. The DFT calculations of gaussian 09 is scalable up to 64 processors, while high-level CCSD(T)-based calculations is only scalable up to 16 processors and require long execustion time. The CPMD is a highly parallelized code and is scalable up to 500 processors. At the moment, the project has four members, Rajeev Assary, Larry Curtiss, Cong Liu, and Stan Zigmunt. We are planning to hire one more postdoc in the near future. Project URL: http://www.anl.gov/catalysis-science/ Current FY Hours Used: undetermined amount New FY Requested allocation: 1200000 Q1: 300000 Q2: 300000 Q3: 300000 Q4: 300000 Justification: We have made excellent use of the previous allocation of 1.2 M core hours. The computations resulted in 11 high impact publications during the 2012-13 allocation time. Significant amount of calculatins were gaussian and CPMD based calculations. gaussian calculations require longer running hours ( often more than 48 hours). Additionally running 10s of gaussian jobs at a time has been found really difficult during the previous allocation. CPMD calculations were performed efficiently on 60 nodes (Fusion). We expect to run similar calculations during this allocation. Thank You, The LCRC Accounts System