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The Electronic States of the Pentatetraene Radical Cation
Author(s) -
Bieri Gerhard,
Dill James D.,
Heilbronner Edgar,
Maier John P.,
Ripoll Jean L.
Publication year - 1977
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19770600235
Subject(s) - chemistry , radical ion , photochemistry , ion , organic chemistry
HeIα excited photoelectron spectra of pentatetraene and the inferred ionization energies are reported. The first band has a characteristic Franck ‐ Condon envelope similar to the first photoelectron bands of allene and butatriene. The four bands found below 16 eV ionization energy have been assigned to the X̃ 2 E, Ã 2 E, B̃ 2 E and C̃ 2 B 2 states of the radical cation of pentatetraene by comparison with STO ‐ 3G and SPINDO calculations on the cumulene series. The correlation scheme includes the 2 s shell ionization energies of ethylene, allene and butatriene. The π‐orbital ionization trends of the cumulenes are discussed in the framework of localized orbitals calculated with the STO ‐ 3G basis set.