Quantum mechanical modeling of the structures, energetics and spectral properties of Iα and Iβ cellulose
Periodic planewave and molecular cluster density functional theory (DFT) calculations were performed on Iα and Iβ cellulose in four different conformations each. The results are consistent with the previous interpretation of experimental X-ray and neutron diffraction data that both Iα and Iβ cellulose are dominantly found in the tg conformation of the hydroxymethyl group with a H-bonding conformation termed “Network A”. Structural and energetic results of the periodic DFT calculations with dispersion corrections (DFT-D2) are consistent with observation suggesting that this methodology is accurate to within a few percent for modeling cellulose. The structural and energetic results were confirmed by comparison of calculated vibrational frequencies against observed infrared and Raman frequencies of Iα and Iβ cellulose. Structures extracted from the periodic DFT-D2 energy minimizations were used to calculate the 13C nuclear magnetic resonance chemical shifts (δ13C), and the tg/Network A conformations of both Iα and Iβ cellulose produced excellent correlations with observed δ13C values.
KeywordsCellulose Infrared Raman NMR DFT
This work was supported by the U.S. Department of Energy grant for the Energy Frontier Research Center in Lignocellulose Structure and Formation (CLSF) from the Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001090. The authors also thank Ilana Bar Ben Gurion University of the Negev for providing IR and Raman frequencies of crystalline cellobiose and Yoshiharu Nishiyama for suggesting DFT-D2 calculations as a methodology for modeling cellulose. Computational support was provided by the Research Computation and Cyberinfrastructure group at The Pennsylvania State University.
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