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

Research output: Contribution to journalArticle

23 Citations (Scopus)

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.

Original languageEnglish (US)
Pages (from-to)909-926
Number of pages18
JournalCellulose
Volume21
Issue number2
DOIs
StatePublished - Jan 1 2014

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Chemical shift
Vibrational spectra
Cellulose
Nuclear magnetic resonance
Hydrogen
Conformations
Water
Adsorption
Hydration
Stretching
Density functional theory
Atoms
Molecules

All Science Journal Classification (ASJC) codes

  • Polymers and Plastics

Cite this

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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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Quantum mechanical calculations on cellulose-water interactions : Structures, energetics, vibrational frequencies and NMR chemical shifts for surfaces of Iα and Iβ cellulose. / Kubicki, James D.; Watts, Heath D.; Zhao, Zhen; Zhong, Linghao.

In: Cellulose, Vol. 21, No. 2, 01.01.2014, p. 909-926.

Research output: Contribution to journalArticle

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T2 - Structures, energetics, vibrational frequencies and NMR chemical shifts for surfaces of Iα and Iβ cellulose

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AU - Watts, Heath D.

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