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Title: New Insights into Hydrogen Bonding and Stacking Interactions in Cellulose

In this quantum chemical study, we explore hydrogen bonding (H-bonding) and stacking interactions in different crystalline cellulose allomorphs, namely cellulose I and cellulose IIII. We consider a model system representing a cellulose crystalline core, made from six cellobiose units arranged in three layers with two chains per layer. We calculate the contributions of intrasheet and intersheet interactions to the structure and stability in both cellulose I and cellulose IIII crystalline cores. Reference structures for this study were generated from molecular dynamics simulations of water-solvated cellulose I and IIII fibrils. A systematic analysis of various conformations describing different mutual orientations of cellobiose units is performed using the hybrid density functional theory (DFT) with the M06-2X with 6-31+G (d, p) basis sets. We dissect the nature of the forces that stabilize the cellulose I and cellulose IIII crystalline cores and quantify the relative strength of H-bonding and stacking interactions. Our calculations demonstrate that individual H-bonding interactions are stronger in cellulose I than in cellulose IIII. We also observe a significant contribution from cooperative stacking interactions to the stabilization of cellulose I . In addition, the theory of atoms-in-molecules (AIM) has been employed to characterize and quantify these intermolecular interactions. AIM analyses highlightmore » the role of nonconventional CH O H-bonding in the cellulose assemblies. Finally, we calculate molecular electrostatic potential maps for the cellulose allomorphs that capture the differences in chemical reactivity of the systems considered in our study.« less
Authors:
 [1]
  1. ORNL
Publication Date:
OSTI Identifier:
1050306
DOE Contract Number:
DE-AC05-00OR22725
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry B; Journal Volume: 115
Research Org:
Oak Ridge National Laboratory (ORNL)
Sponsoring Org:
ORNL Program Development
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; BONDING; CELLOBIOSE; CELLULOSE; CHAINS; ELECTROSTATICS; FUNCTIONALS; HYDROGEN; STABILITY; STABILIZATION