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Electronic Structure of Long Polyenes: States and Transition Dipoles

Published online by Cambridge University Press:  25 February 2011

Bryan E. Kohler
Bryan E. Kohler*
Affiliation:
Chemistry Department, University of California, Riverside, CA 92521, U.S.A.
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Abstract

Electronic excitation energies and transition dipoles measured for symmetrically substituted linear polyenes (R-(CH=CH)N-R) with chain lengths n ranging from 2 to 8 are well fit by the functional form A+B/N. Extrapolation to the long chain limit correlates the band gap transition of polyacetylene with the polyene 11Ag to 11Bu transition. The amount by which the highly correlated polyene 21Ag state is lower than the 11Bu state increases with increasing chain length, extrapolating to roughly half of the 11Bu excitation energy. The 11Ag to 11Bu transition dipole magnitude per chain repeat unit attains a maximum value of 3.0 Debye at an effective conjugation length 5 double bonds.

Careful studies on linear polyenes provides insight into the electronic structure of polyacetylene.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 173: Symposium Q – Advanced Organic Solid State Materials , 1989 , 649
Copyright
Copyright © Materials Research Society 1990

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References

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