Premium
Ab Initio and Molecular Mechanics Study of Conformational Selectivity of Chlorinated Compounds Adsorbed in the Clathrate Phase of Syndiotactic Polystyrene. The Role of Electrostatic Host‐Guest Interactions
Author(s) -
Milano Giuseppe,
Guerra Gaetano,
Cavallo Luigi
Publication year - 2001
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/1521-3919(20010401)10:4<349::aid-mats349>3.0.co;2-f
Subject(s) - chemistry , van der waals force , ab initio , conformational isomerism , chemical physics , polystyrene , clathrate hydrate , molecular mechanics , computational chemistry , tacticity , electrostatics , adsorption , phase (matter) , molecular dynamics , molecule , polymer , organic chemistry , hydrate , polymerization
A computational study of the conformational selectivity of some chlorinated compounds adsorbed in polymeric clathrates of syndiotactic polystyrene is presented. Ab initio investigation of the model complex benzene/CH 3 Cl gives information about the role of electrostatic interactions in determining the favored molecular orientations. The changes of conformational equilibria of some chlorinated compounds upon clathration have been rationalized by a molecular mechanics approach. This shed light on the nature of the host‐guest interactions: although van der Waals interactions are most relevant for the sorption process, the observed conformations are essentially associated with electrostatic interactions of the guest conformers with a substantially quadrupolar electrostatic field of the crystalline cavity.