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Die Photoelektron‐Spektren der Monohalogenacetylene
Author(s) -
Haink H. J.,
Heilbronner E.,
Hornung V.,
KlosterJensen Else
Publication year - 1970
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.19700530522
Subject(s) - chemistry , ionization , spectral line , halogen , atomic orbital , atomic physics , physics , electron , ion , quantum mechanics , alkyl , organic chemistry
The photoelectron spectra of the four monohaloacetylenes XCCH with X F, Cl, Br, I have been recorded. The first four bands of these spectra are assigned (in order of increasing ionization potentials) to the following states: band 1: 2 Π 3/2 (1), 2 Π 1/2 (1); band 2: 2 Π 3/2 (2), 2 Π 1/2 (2); band 3: 2 Σ + (3); band 4: 2 Σ + (4). A correlation diagram based on a simple ZDO‐MO model shows that the observed band positions and the size of the splits due to spin‐orbit coupling can be satisfactorily explained in terms of such a model. It is found that the orbital energies A X of the postulated halogen n p λ(X)‐basis orbitals are a linear function of the ionization potentials I (X) of the free atoms X. The validity of the ZDO‐MO‐model is confirmed by the excellent qualitative agreement between the observed and predicted spacings of the vibrational fine structure of the π‐bands.