Premium
Photoelectron Spectra of Azabenzenes and Azanaphthalenes: I. Pyridine, diazines, s ‐triazine and s ‐tetrazine
Author(s) -
Gleiter R.,
Heilbronner E.,
Hornung V.
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.19720550130
Subject(s) - chemistry , pyridazine , tetrazine , pyrazine , atomic orbital , spectral line , lone pair , computational chemistry , crystallography , molecular orbital , pyrimidine , basis (linear algebra) , parametrization (atmospheric modeling) , atomic physics , molecular physics , stereochemistry , quantum mechanics , physics , molecule , geometry , organic chemistry , electron , mathematics , radiative transfer
The experimental and theoretical basis of a recently proposed reassignment of the bands in the PE. spectra of pyridine, pyridazine, pyrimidine and pyrazine is discussed in detail. A characteristic feature of the derived orbital sequence is that it takes the ‘through‐space’ and ‘through‐bond’ interaction between the ‘lone pair’ basis orbitals explicitly into account. A simple parametrization of the orbital energies, based on HMO‐type models for the π‐orbitals and for the ‘lone pair’ linear combinations, yields excellent agreement with the observed band positions in the PE. spectra of s ‐triazine and s ‐tetrazine. Our new assignment is compared to those proposed previously.