Cellulose

, Volume 21, Issue 2, pp 909–926 | Cite as

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

  • James D. Kubicki
  • Heath D. Watts
  • Zhen Zhao
  • Linghao Zhong
Original Paper

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.

Keywords

Density functional theory Nuclear magnetic resonance Surface Infrared Raman Water 

Supplementary material

10570_2013_29_MOESM1_ESM.docx (3.9 mb)
Supplementary material 1 (DOCX 3967kb)

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Copyright information

© Springer Science+Business Media Dordrecht 2013

Authors and Affiliations

  • James D. Kubicki
    • 1
  • Heath D. Watts
    • 1
  • Zhen Zhao
    • 1
  • Linghao Zhong
    • 2
  1. 1.Department of GeosciencesThe Pennsylvania State UniversityUniversity ParkUSA
  2. 2.Department of ChemistryThe Pennsylvania State UniversityMont AltoUSA

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