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

Phys Chem Chem Phys. 2005 Sep 21;7(18):3284-9. doi: 10.1039/b507882m. Epub 2005 Aug 12.

Abstract

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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Algorithms*
  • Cross-Linking Reagents
  • Models, Chemical*
  • Polyenes / chemistry*
  • Static Electricity
  • Structure-Activity Relationship

Substances

  • Cross-Linking Reagents
  • Polyenes