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Title: Photoelectron Wave Function in Photoionization: Plane Wave or Coulomb Wave?

Abstract

The calculation of absolute total cross sections requires accurate wave functions of the photoelectron and of the initial and final states of the system. The essential information contained in the latter two can be condensed into a Dyson orbital. We employ correlated Dyson orbitals and test approximate treatments of the photoelectron wave function, that is, plane and Coulomb waves, by comparing computed and experimental photoionization and photodetachment spectra. We find that in anions, a plane wave treatment of the photoelectron provides a good description of photodetachment spectra. For photoionization of neutral atoms or molecules with one heavy atom, the photoelectron wave function must be treated as a Coulomb wave to account for the interaction of the photoelectron with the +1 charge of the ionized core. For larger molecules, the best agreement with experiment is often achieved by using a Coulomb wave with a partial (effective) charge smaller than unity. This likely derives from the fact that the effective charge at the centroid of the Dyson orbital, which serves as the origin of the spherical wave expansion, is smaller than the total charge of a polyatomic cation. Finally, the results suggest that accurate molecular photoionization cross sections can be computed withmore » a modified central potential model that accounts for the nonspherical charge distribution of the core by adjusting the charge in the center of the expansion.« less

Authors:
 [1];  [1];  [2];  [3];  [2];  [1]
+ Show Author Affiliations
  1. Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, United States
  2. Institute for Theoretical Chemistry, Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712, United States
  3. Combustion Research Facility, Sandia National Laboratories, Livermore, California 94551, United States
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1250177
Alternate Identifier(s):
OSTI ID: 1341397
Report Number(s):
SAND-2016-10082J
Journal ID: ISSN 1948-7185
Grant/Contract Number:  
FG02-05ER15685; FG02-07ER15884; AC04-94AL85000
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Name: Journal of Physical Chemistry Letters Journal Volume: 6 Journal Issue: 22; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; cross sections; Dyson orbital; effective charge; EOM-CC; Franck−Condon factors; photodetachment

Citation Formats

Gozem, Samer, Gunina, Anastasia O., Ichino, Takatoshi, Osborn, David L., Stanton, John F., and Krylov, Anna I. Photoelectron Wave Function in Photoionization: Plane Wave or Coulomb Wave?. United States: N. p., 2015. Web. doi:10.1021/acs.jpclett.5b01891.
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Gozem, Samer, Gunina, Anastasia O., Ichino, Takatoshi, Osborn, David L., Stanton, John F., & Krylov, Anna I. Photoelectron Wave Function in Photoionization: Plane Wave or Coulomb Wave?. United States. https://doi.org/10.1021/acs.jpclett.5b01891
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Gozem, Samer, Gunina, Anastasia O., Ichino, Takatoshi, Osborn, David L., Stanton, John F., and Krylov, Anna I. Wed . "Photoelectron Wave Function in Photoionization: Plane Wave or Coulomb Wave?". United States. https://doi.org/10.1021/acs.jpclett.5b01891.
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@article{osti_1250177,
title = {Photoelectron Wave Function in Photoionization: Plane Wave or Coulomb Wave?},
author = {Gozem, Samer and Gunina, Anastasia O. and Ichino, Takatoshi and Osborn, David L. and Stanton, John F. and Krylov, Anna I.},
abstractNote = {The calculation of absolute total cross sections requires accurate wave functions of the photoelectron and of the initial and final states of the system. The essential information contained in the latter two can be condensed into a Dyson orbital. We employ correlated Dyson orbitals and test approximate treatments of the photoelectron wave function, that is, plane and Coulomb waves, by comparing computed and experimental photoionization and photodetachment spectra. We find that in anions, a plane wave treatment of the photoelectron provides a good description of photodetachment spectra. For photoionization of neutral atoms or molecules with one heavy atom, the photoelectron wave function must be treated as a Coulomb wave to account for the interaction of the photoelectron with the +1 charge of the ionized core. For larger molecules, the best agreement with experiment is often achieved by using a Coulomb wave with a partial (effective) charge smaller than unity. This likely derives from the fact that the effective charge at the centroid of the Dyson orbital, which serves as the origin of the spherical wave expansion, is smaller than the total charge of a polyatomic cation. Finally, the results suggest that accurate molecular photoionization cross sections can be computed with a modified central potential model that accounts for the nonspherical charge distribution of the core by adjusting the charge in the center of the expansion.},
doi = {10.1021/acs.jpclett.5b01891},
journal = {Journal of Physical Chemistry Letters},
number = 22,
volume = 6,
place = {United States},
year = {Wed Nov 04 00:00:00 EST 2015},
month = {Wed Nov 04 00:00:00 EST 2015}
}
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https://doi.org/10.1021/acs.jpclett.5b01891
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