TY - JOUR
T1 - Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments
AU - Truhlar, Donald G.
AU - Hiberty, Philippe C.
AU - Shaik, Sason
AU - Gordon, Mark S.
AU - Danovich, David
N1 - Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/9/2
Y1 - 2019/9/2
N2 - 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.
AB - 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.
KW - Dyson orbital
KW - Koopmans’ theorem
KW - electron momentum spectroscopy
KW - localized orbitals
KW - photoelectron spectroscopy
UR - http://www.scopus.com/inward/record.url?scp=85068497314&partnerID=8YFLogxK
U2 - 10.1002/anie.201904609
DO - 10.1002/anie.201904609
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C2 - 31081208
AN - SCOPUS:85068497314
SN - 1433-7851
VL - 58
SP - 12332
EP - 12338
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 36
ER -