Intermolecular interactions in pi -conjugated systems: Application to polyenes

Albert, IDL and Ramasesha, S (1989) Intermolecular interactions in pi -conjugated systems: Application to polyenes. In: Physical Review B: Condensed Matter, 40 (12). pp. 8516-8521.

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Abstract

A computational scheme has been developed for strongly interacting systems wherein the intermolecular interaction is introduced as a charge-induced-dipole term. Within this approximation, the model Hamiltonian is exactly solved using a valence-bond basis. The validity of the scheme has been checked by use of exact calculations on small model systems. The method has been applied to finite polyenes to study the shifts in the ground-state energies and dipole-allowed excited-state energies in the presence of neighbors. Our calculations show a red shift in the optical gap of the infinite polyene by 0.124 eV, which is rather small compared to the experimental red shift. This is traced to the larger inaccuracy in the calculated shift in the excited state. The calculated shift in the ground-state energies are more accurate and hence the method is better suited for studying the effect of intermolecular interactions on the properties of the ground state.

Item Type:	Journal Article
Publication:	Physical Review B: Condensed Matter
Publisher:	The American Physical Society
Additional Information:	Copyright of this article belongs to The American Physical Society.
Department/Centre:	Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited:	03 Aug 2010 04:56
Last Modified:	19 Sep 2010 06:12
URI:	http://eprints.iisc.ac.in/id/eprint/30956

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