Ab initio studies of cellulose I: Crystal structure, intermolecular forces, and interactions with water

Yan Li, Milo Lin, James W. Davenport

Research output: Contribution to journalArticle

51 Citations (Scopus)

Abstract

We have studied the structural, energetic, and electronic properties of crystalline cellulose I using first-principles density functional theory (DFT) with semiempirical dispersion corrections. The predicted crystal structures of both Iα and Iβ phases agree well with experiments and are greatly improved over those predicted by DFT within the local and semilocal density approximations. The cohesive energy is analyzed in terms of interchain and intersheet interactions, which are calculated to be of similar magnitude. Both hydrogen bonding and van der Waals (vdW) dispersion forces are found to be responsible for binding cellulose chains together. In particular, dispersion corrections prove to be indispensable in reproducing the equilibrium intersheet distance and binding strength; however, they do not improve the underestimated hydrogen bond length from DFT. The computed energy gaps of crystalline cellulose are 5.7 eV (Iα) and 5.4 eV (Iβ), whereas localized surface states appear within the gap for surfaces. The interaction of cellulose with water is studied by investigating the adsorption of a single water molecule on the hydrophobic Iβ(100) surface. The formation of hydrogen bond at the water/cellulose interface is shown to depend sensitively on the adsorption site for example above the equatorial hydroxyls or the CH moieties pointing out of the cellulose sheets. VdW dispersion interactions also contribute significantly to the adsorption energy.

Original languageEnglish (US)
Pages (from-to)11533-11539
Number of pages7
JournalJournal of Physical Chemistry C
Volume115
Issue number23
DOIs
StatePublished - Jun 16 2011

Fingerprint

intermolecular forces
cellulose
Cellulose
Crystal structure
crystal structure
Water
water
Density functional theory
Hydrogen bonds
interactions
density functional theory
Adsorption
adsorption
hydrogen bonds
Crystalline materials
Bond length
Surface states
Electronic properties
Hydroxyl Radical
Energy gap

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Ab initio studies of cellulose I : Crystal structure, intermolecular forces, and interactions with water. / Li, Yan; Lin, Milo; Davenport, James W.

In: Journal of Physical Chemistry C, Vol. 115, No. 23, 16.06.2011, p. 11533-11539.

Research output: Contribution to journalArticle

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