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Model calculations of polarizabilities of polyene chains: Oligomers and infinite polymers
Author(s) -
Champagne Benoit,
André JeanMarie
Publication year - 1990
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/qua.560382484
Subject(s) - polyene , polarizability , resolvent , chemistry , propagator , polarization (electrochemistry) , computational chemistry , basis set , molecular physics , quantum mechanics , physics , molecule , mathematics , mathematical analysis , density functional theory , organic chemistry
In order to find the best methods for calculating the (hyper) polarizabilities of long oligomers and infinite polymers, we first propose in this paper to calculate the linear static electric polarizabilities of regular and alternant polyene chains by using the Hückel approach. For these calculations, the perturbation approach is used to obtain second‐order response properties. We have derived this formulation by starting from the polarization propagator within an approximation which consists of projecting the superoperator resolvent form on a basis set of operators composed of only single excitations. For polyenes of different degrees of bond alternation, we obtained in the same Hückel approximation the asymptotic value of the polarizability per unit cell by using the Bloch functions in the Genkin and Mednis technique of calculating polymeric polarizabilities.