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Quantum mechanical calculations on cellulose–water interactions: structures, energetics, vibrational frequencies and NMR chemical shifts for surfaces of Iα and Iβ cellulose

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Abstract

Periodic and molecular cluster density functional theory calculations were performed on the Iα (001), Iα (021), Iβ (100), and Iβ (110) surfaces of cellulose with and without explicit H2O molecules of hydration. The energy-minimized H-bonding structures, water adsorption energies, vibrational spectra, and 13C NMR chemical shifts are discussed. The H-bonded structures and water adsorption energies (ΔEads) are used to distinguish hydrophobic and hydrophilic cellulose–water interactions. O–H stretching vibrational modes are assigned for hydrated and dry cellulose surfaces. Calculations of the 13C NMR chemical shifts for the C4 and C6 surface atoms demonstrate that these δ13C4 and δ13C6 values can be upfield shifted from the bulk values as observed without rotation of the hydroxymethyl groups from the bulk tg conformation to the gt conformation as previously assumed.

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Acknowledgments

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 Yoshiharu Nishiyama for suggesting DFT-D2 calculations as a methodology for modeling cellulose. We also acknowledge discussions with Roger Newman and Mike Jarvis as well as numerous CLSF participants that improved the manuscript. Computational support was provided by the Research Computation and Cyberinfrastructure group at The Pennsylvania State University.

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  1. Department of Geosciences, The Pennsylvania State University, University Park, PA, 16802, USA

    James D. Kubicki, Heath D. Watts & Zhen Zhao

  2. Department of Chemistry, The Pennsylvania State University, Mont Alto, PA, 17237, USA

    Linghao Zhong

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  1. James D. Kubicki
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  2. Heath D. Watts
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Correspondence to James D. Kubicki.

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Kubicki, J.D., Watts, H.D., Zhao, Z. et al. Quantum mechanical calculations on cellulose–water interactions: structures, energetics, vibrational frequencies and NMR chemical shifts for surfaces of Iα and Iβ cellulose. Cellulose 21, 909–926 (2014). https://doi.org/10.1007/s10570-013-0029-x

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