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On the Correlation between Photoelectron and Electronic Spectra. Part. II : Experimental indications about the shape of lone pair orbitals
Author(s) -
Haselbach E.,
Schmelzer A.
Publication year - 1972
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.19720550533
Subject(s) - chemistry , lone pair , atomic orbital , heteroatom , ionization , symmetry (geometry) , atomic physics , molecular orbital , ionization energy , molecular physics , computational chemistry , quantum mechanics , molecule , ring (chemistry) , physics , ion , electron , geometry , mathematics , organic chemistry
For a π‐molecular system containing two symmetry‐equivalent heteroatoms, a qualitative relationship between the difference in the n ‐ionization potentials (Δ IP ) and the difference between the n → π* excitation energies (ΔΔ E ) is derived, using semi‐localized orbitals as a basis. The comparison between Δ IP and ΔΔ E yields information about the energies and/or the shapes of the two lone pair MO's in the model system. The results provide further insight into ‘through space’ and ‘through bond’ interaction concept introduced by Hoffmann .