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Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments
Author(s) -
Truhlar Donald G.,
Hiberty Philippe C.,
Shaik Sason,
Gordon Mark S.,
Danovich David
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201904609
Subject(s) - delocalized electron , molecular orbital theory , molecular orbital , linear combination of atomic orbitals , atomic orbital , atomic physics , chemistry , chemical physics , localized molecular orbitals , electron , physics , molecular physics , molecule , quantum mechanics
Electron momentum spectroscopy, scanning tunneling microscopy, and photoelectron spectroscopy provide unique information about electronic structure, but their interpretation has been controversial. This essay discusses a framework for interpretation. Although this interpretation is not new, we believe it is important to present this framework in light of recent publications. The key point is that these experiments provide information about how the electron distribution changes upon ionization, not how electrons behave in the pre‐ionized state. Therefore, these experiments do not lead to a “selection of the correct orbitals” in chemistry and do not overturn the well‐known conclusion that both delocalized molecular orbitals and localized molecular orbitals are useful for interpreting chemical structure and dynamics. The two types of orbitals can produce identical total molecular electron densities and therefore molecular properties. Different types of orbitals are useful for different purposes.