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 Other Systems: CNM Argonne, Blue Gene/P Argonne Science: This work will be done as part of the new Energy Frontier Research center at Argonne and will be done in close collaboration with the experimental part of the Center involving researchers from Argonne, Northwestern University, Purdue University, and the University of Wisconsin. Efficient chemical transformation of biomass is essential to produce sustainable energy and industrial chemicals. Industrial level chemical conversion of naturally abundant sugar molecules to alternative fuel precursor chemicals (hydroxyl-methyl-furfural, γ-valero-lactone, levulinic acid) require accurate molecular level understanding of reaction energetics and kinetics. High-level quantum chemical methods can provide accurate energetics for important chemical transformations of sugar molecules and assist experimental efforts for efficient production of alternative fuels and fuel precursors. Kinetics and thermodynamics of complex sugar decomposition pattern is another area of huge importance that requires fundamental understanding to limit undesired reactions. Due to development of fast computers and reliable, accurate computational methods now allows us to compute the energetics of many important reactions in the Biomass conversion. Micro-kinetic modeling of various reactio ns based from accurate ab-initio calculations is another useful area and need a great deal of computational studies. Industrial level chemical transformation of biomass to useful chemicals requires sustainable, efficient and economical catalysts and this require design of multifunctional catalysts. Mineral or Lewis acid catalyzed reaction is envisioned for the conversion of glucose to hydroxy-methyl-furfural, levulinic acid, γ-valero-lactone and this require detailed understanding of possible reactions of sugar molecules with a variety of acid sites and elucidation of reaction mechanisms Computational modeling of catalyst design, binding modes of sugar molecules and reaction sequences are essential to compliment experimental efforts towards an industrial level biomass conversion Project description: Biomass has the potential to serve as sustainable source of energy and organic carbon for our industrialized society. The key reactions involve the process of the converting the biomass to useful chemicals are hydrolysis, dehydration, isomerization, aldol condensation, reforming, hydrogenation, and oxidation. Investigating these important reactions and modeling efficient catalysts for industrial use, by using computational chemistry methods is the aim of this project. Acid-Base hydrolysis and pyrolysis techniques are currently practiced as the ways to convert biomass to useful platform chemicals. These decomposition reactions are typically complex; include structural rearrangements, dehydration, oxidation and reduction. In order to assess the accurate kinetic and thermodynamic feasibilities of possible reactions, computational modeling is alternative approach to experiments. Application of methods such as G4/G4MP2, a CCSD(T) based energy evaluation method has been employed in the recent past to gain accurate understanding of energetics along with the help of density functional methods to investigate structures. Due to the complex chemical pathways of reactions in the biomass conversion, micro-kinetic models would be more appropriate and needed to assist the experimental interpretations or predict the outcome of such chemical transformations. This would require a significant amount of computational resources. Development of possible micro-k inetic models for following reactions would enhance the fundamental understanding of biomass catalysis: • Acid hydrolysis and Pyrolysis of Glucose • Acid hydrolysis and Pyrolysis of Sucrose • Acid hydrolysis and Pyrolysis of Cellobiose/triose • Understanding the Oligomerization processes during hydrolysis and pyrolysis These studies would lead to building of a thermochemical database and can be used as future reference tool for the thermodynamics for biomass transformations. And computational modeling of these reactions would also enable us to understand the mechanistic details at the atomistic level. Project URL: http://www.anl.gov/catalysis-science/ Current FY Hours Used: undetermined amount New FY Requested allocation: 600000 Q1: 150000 Q2: 150000 Q3: 150000 Q4: 150000 Justification: We gratefully acknowledge the grants for the computer time during the past two years. We have acknowledged LCRC for the computational resources. The following are the list of publications. 1. R.S. Assary, P. Redfern, J. Greeley, L. A Curtiss (2011). Mechanistic insights into the decomposition of fructose to hydroxy-methyl-furfural in neutral and acid environments using high-level quantum chemical methods, 4341-4349. In Journal of Physical Chemistry B. 2. R.S Assary, L.A Curtiss (2011). Theoretical Study of 1,2-Hydride Shift Associated with the Isomerization of Glyceraldehyde to Dihydroxy Acetone by Lewis Acid Active Site Models. In The journal of Physical Chemistry A. 8754-61 3. R.S, Assary, L. A Curtiss (2011). Thermochemistry and reaction barriers for the formation of Levoglucosenone from Cellobiose. Accepted, ChemCatChem (cctc.201100280). 4. T Kim, R. S. Assary, C. Marshall, L.A. Curtiss, P. Stair (2011). Acid Catalyzed Polymerization of Furfuryl alcohol : Combined experimental and Theoretical Study. In ChemCatChem (Cover story), Volume 3, 1369 5. T Kim, R.S. Assary, L.A. Curtiss, C. Marshal, P. Stair (2011). Vibrational properties of levulinic acid and furan derivatives: Raman spectroscopy and theoretical calculations. In Journal of Raman Spectroscopy. (Published Feb 2011,DOI 10.1002/jrs.2951) 6. R.S. Assary, P. Redfern, J. Hammond, J. Greeley, L.A. Curtiss (2010) Computational Studies of the Thermochemistry for Conversion of Glucose to Levulinic Acid. In Journal of Physical Chemistry B. 9002-9009 7. R.S. Assary, P. Redfern, J. Hammond, J. Greeley, L.A. Curtiss (2010) Predicted Thermochemistry for Chemical Conversion of 5-hydroxymethylfurfural. In Chemical Physics Letters. 123-128. Thank You, The LCRC Accounts System