title: Effects of water on the structure and bonding of resorcinol in the interlayer of montmorillonite nanocomposite: a periodic first principle study.
abstract: Resorcinol forms a novel nanocomposite in the interlayer of montmorillonite. This resorcinol oligomer is stable inside the clay matrixes even above the boiling point of the monomer. A periodic ab initio calculation was performed with hydrated and nonhydrated montmorillonite before and after intercalation of resorcinol. For the most feasible dimer and tetramer shaped oligomer of resorcinol, the intramolecular and intermolecular hydrogen bonding feasibility has been tested using the DFT-BLYP approach and the DNP basis set in the gas phase and in the presence of aqueous solvent. After locating the active site through Fukui functions within the helm of the hard-soft acid-base principle, the relative nucleophilicity of the active cation sites in their hydrated state has been calculated. A novel quantitative scale in terms of the relative nucleophilicity and electrophilicity of the interacting resorcinol oligomers before and after solvation is proposed. Besides that, a comparison with a hydration situation and also the strength of the hydrogen bridges have been evaluated using mainly the dimer and cyclic tetramer type oligomers of resorcinol. Using periodic ab initio calculations, the formation mechanism was traced by the following two ways: (1) resorcinol molecules combine without any interaction with water or (2) resorcinol oligomerizes through water. Both the mechanism is compared and the effect of water on the process is elucidated. The results show that resorcinol molecules combine after hydration only and hence they are stable at higher temperature. The fittings of the oligomers were also tested as well by periodic calculation to compare the stability of the oligomers inside the newly formed clay nanocomposite.
authors.affiliation: Accelrys K.K., Nishishinbashi TS Building 11F, 3-3-1 Nishishinbashi, Minato-ku, Tokyo 105-0003, Japan. c-abhijit@aist.go.jp
authors.forename: Abhijit
authors.initials: A
authors.lastname: Chatterjee
authors.forename: Takeo
authors.initials: T
authors.lastname: Ebina
authors.forename: Fujio
authors.initials: F
authors.lastname: Mizukami