(712f) Prediction of Elementary Reactions for Pyrolysis of Glucose

Pyrolysis kinetics for the monosaccharide β-glucose are of interest directly and because of their possible relation to the pyrolysis kinetics of cellulose, for which β-glucose is the monomer. We describe the experimental and computational-chemistry background literature and our recent calculations for isomerization and conversion to levoglucosan, a principal product. CBS-QB3 model chemistry is used for final energies, although B3LYP/6-31G(d,p) calculations are used for initial optimizations. Certain initial transition-state searches are performed without nonparticipating OH groups for effective use of computing resources. Both gas-phase and solvated structures are considered. We show that pericyclic steps are keys to explaining for these non-ionic reactions.

We gratefully acknowledge support of this research by the U.S. Department of Energy, Office of Science, through the Catalysis Center for Energy Innovation EFRC, based at the University of Delaware. This work was partially supported by the National Center for Supercomputing Applications under grant number TG-CHE100121 "Development of Reactive Molecular Dynamics and Reaction Thermochemistry for Lignocellulosic Biofuel Production" and used the Pople supercomputer.