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Excess polarizabilities upon the first dipole‐allowed excitation of some conjugated oligomers
Author(s) -
Ye J. F.,
Chen H.,
Note R.,
Mizuseki H.,
Kawazoe Y.
Publication year - 2008
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1378
Subject(s) - chemistry , polarizability , time dependent density functional theory , excited state , dipole , density functional theory , excitation , polarizable continuum model , conjugated system , ground state , computational chemistry , molecule , molecular physics , atomic physics , quantum mechanics , solvation , physics , organic chemistry , polymer
Abstract This paper presents theoretical predictions for the excess polarizabilities upon excitation from the ground state to the first dipole‐allowed excited state (1 1 B u ) of some conjugated oligomers. The excess polarizability was obtained by simulating the Stark shift, which was predicted by the time‐dependent density functional theory (TDDFT) with the hybrid Becke‐3 Lee–Yang–Parr (B3LYP) potential. The Stark shift in solution was simulated by employing the non‐equilibrium integral equation formalism polarizable continuum model (IEFPCM). All the model molecules considered in this study were fully optimized by the Hartree–Fock (HF) method and the density functional theory (DFT) with the B3LYP potential, respectively. For diphenylpolyenes, the excess polarizabilities displayed by the DFT/B3LYP‐optimized geometries are more reasonable than those displayed by the HF‐optimized geometries when compared with the experimental results. However, this feature is not clearly demonstrated by our results in the cases of oligo(phenylenevinylene)s (OPVs). Copyright © 2008 John Wiley & Sons, Ltd.