Premium
Molecular orbital approach to the Peierls instability in polyenes and its application to model crystals of charge‐transfer complexes
Author(s) -
Aoki Yuriko,
Tada Tomofumi,
Imamura Akira
Publication year - 1997
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1997)64:3<325::aid-qua5>3.0.co;2-y
Subject(s) - polyene , chemistry , crystal (programming language) , molecule , intermolecular force , charge (physics) , instability , chemical physics , molecular orbital , equidistant , crystal structure , molecular physics , crystallography , computational chemistry , physics , quantum mechanics , computer science , geometry , mathematics , organic chemistry , programming language
We have already proposed a convenient method to estimate themagnitude of the Peierls instability in finite one‐ and two‐dimensional (1Dand 2D) polyenes from the viewpoint of orbital symmetry [J. Chem.Phys., 103 , 9726 (1995)]. This treatment isapplied to a model system for charge‐transfer complexes, in which theunpaired electron is occupied in a molecule, generating a half‐filledenergy band by intermolecular interaction. As the first step, a modelmolecular crystal composed of ethylene anion (or cation) molecules istreated to confirm the applicability of our formulas for 2D polyene. It isclearly shown that molecules in a crystal are structurally distorted togain the energetic stabilization within the 1D structure, while they arerearranged in a regularly equidistant structure under strong interchaininteraction. This treatment would provide insight into the relationshipbetween the crystal structure of charge‐transfer complexes and itselectronic property. © 1997 John Wiley & Sons, Inc. Int JQuant Chem 64 : 325–336, 1997