title: Model of the cooperative rearranging region for polyhydric alcohols.
abstract: A simplified model of a hydrogen-bonding network is proposed in order to clarify the microscopic structure of the cooperative rearranging region (CRR) in Adam-Gibbs theory [G. Adam and J. H. Gibbs, J. Chem. Phys. 43, 139 (1965)]. Our model can be solved analytically, and it successfully explains the reported systematic features of the glass transition of polyhydric alcohols. In this model, hydrogen bonding is formulated based on binding free energy. Assuming a cluster of molecules connected by double hydrogen bonds is a CRR and approximating the hydrogen-bonding network as a Bethe lattice in percolation theory, the temperature dependence of the structural relaxation time can be obtained analytically. Reported data on relaxation times are well described by the obtained equation. By taking the lower limit of the binding free energy with this equation, the Vogel-Fulcher-Tammann equation can be derived. Consequently, the fragility index and glass transition temperature can be expressed as functions of the number of OH groups in a molecule, and this relation agrees well with the reported experimental data.
authors.affiliation: Department of Chemistry, University of Tennessee, Knoxville, TN 37996-1600, USA.
authors.forename: Masahiro
authors.initials: M
authors.lastname: Nakanishi
authors.forename: Ryusuke
authors.initials: R
authors.lastname: Nozaki
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D002241:Carbohydrates / Q000737:chemistry; D002621:Chemistry / Q000379:methods; D005898:Glass; D006860:Hydrogen Bonding; D008968:Molecular Conformation; D013696:Temperature; D013816:Thermodynamics; D044366:Transition Temperature; D014867:Water / Q000737:chemistry
chemical_list: D000438:Alcohols; D002241:Carbohydrates; D014867:Water