Modeling the electric field third-order nonlinear responses of an infinite aggregate of hexatriene chains using the electrostatic interaction model.
A classical electrostatic polarization scheme using the additive distribution procedure has been applied to determine the static longitudinal polarizability and second hyperpolarizability of a all-trans hexatriene molecule in an infinite stretched fiber. The parameters have been derived from ab initio coupled-perturbed Hartree-Fock calculations and the electrostatic scheme has been validated via comparison with ab initio results on small clusters. Upon packing, the polarizability of all-trans hexatriene increases by 7% whereas the second hyperpolarizability increases by as much as 61%. These increases result from the balance between the enhancement of the (hyper)polarizability due to collinear packing and the reduction associated with lateral packing.
Guillaume
Maxime
M
Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000, Namur, Belgium.
Champagne
Benoît
B
D000465:Algorithms; D003432:Cross-Linking Reagents; D008956:Models, Chemical; D011090:Polyenes / Q000737:chemistry*; D055672:Static Electricity; D013329:Structure-Activity Relationship
D003432:Cross-Linking Reagents; D011090:Polyenes