Modelisation of the Electric Field Linear Response of an Infinite Aggregate of All-Trans Hexatriene Chains by Electrostatic Interaction Model

Modeling the electric field third-order nonlinear responses of an infinite aggregate of hexatriene chains using the electrostatic interaction model

“…On the other hand, for n > ¼ 1, the longitudinal polarizability increases by up to 19% for n J ¼ 29. This is consistent with the original works due to Silberstein 17 and Applequist et al 18 as well as with previous investigations on model systems, [24][25][26][27][28][29][30] showing that, as a result of the different screening fields, the polarizability increases along the direction of packing while it decreases in the perpendicular direction. For any value of n > the polarizability of the reference (central) molecule converges rapidly with n J though the convergence is slower for thicker bundles.…”

“…4 This work concerns the linear and third-order nonlinear responses of models of all-trans polyacetylene (PA) fibers, which have already been the subject of several investigations. [24][25][26][27][28][29][30] Initially, using ab initio Hartree-Fock as well as correlated approaches, Kirtman 24 reported that interactions between nearest-neighboring butadienes and hexatrienes lead to a substantial decrease of the longitudinal electronic second hyperpolarizability. Similar conclusions were later drawn for the vibrational second hyperpolarizability of aggregates containing up to five chains of short polyenes.…”