Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments
Abstract
Abstract 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.
- Authors:
-
[1];
[2];
[3];
[4];
[3]
- Department of Chemistry Chemical Theory Center, and Minnesota Supercomputing Institute University of Minnesota 207 Pleasant St. SE Minneapolis MN 55455-0431 USA
- Laboratoire de Chimie Physique, CNRS UMR8000, Bat. 349 Université de Paris-Sud 91405 Orsay Cédex France
- Institute of Chemistry The Hebrew University of Jerusalem Givant-Ram Campus Jerusalem 9190407 Israel
- Department of Chemistry Iowa State University and Ames Laboratory Ames IA 50014 USA
- Publication Date:
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1531182
- Resource Type:
- Publisher's Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition) Journal Volume: 58 Journal Issue: 36; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
Citation Formats
Truhlar, Donald G., Hiberty, Philippe C., Shaik, Sason, Gordon, Mark S., and Danovich, David. Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments. Germany: N. p., 2019.
Web. doi:10.1002/anie.201904609.
Truhlar, Donald G., Hiberty, Philippe C., Shaik, Sason, Gordon, Mark S., & Danovich, David. Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments. Germany. https://doi.org/10.1002/anie.201904609
Truhlar, Donald G., Hiberty, Philippe C., Shaik, Sason, Gordon, Mark S., and Danovich, David. Fri .
"Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments". Germany. https://doi.org/10.1002/anie.201904609.
@article{osti_1531182,
title = {Orbitals and the Interpretation of Photoelectron Spectroscopy and (e,2e) Ionization Experiments},
author = {Truhlar, Donald G. and Hiberty, Philippe C. and Shaik, Sason and Gordon, Mark S. and Danovich, David},
abstractNote = {Abstract 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.},
doi = {10.1002/anie.201904609},
journal = {Angewandte Chemie (International Edition)},
number = 36,
volume = 58,
place = {Germany},
year = {Fri Jul 05 00:00:00 EDT 2019},
month = {Fri Jul 05 00:00:00 EDT 2019}
}
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