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On the adequacy of the molecular‐orbital picture for describing ionization processes
Author(s) -
Cederbaum L. S.,
Schirmer J.,
Domcke W.,
Von Niessen W.
Publication year - 1978
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560140506
Subject(s) - ionization , acetylene , molecular orbital , chemistry , ionization energy , atomic physics , valence (chemistry) , electron , core electron , valence electron , molecular orbital theory , computational chemistry , molecule , physics , ion , nuclear physics , organic chemistry
General arguments concerning the adequacy of the molecular‐orbital ( MO ) ionization picture are given. Whereas the MO ionization picture is found to be valid for both outer valence and core electrons, it may completely break down in the inner valence region. The general considerations are supported by many‐body calculations on methane, acetylene, hydrogen cyanide, and dinitrogen tetroxide. It is demonstrated that the breakdown of the MO ionization picture is a common phenomenon.