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Title: Characterizing bonding patterns in diradicals and triradicals by density-based wave function analysis: A uniform approach

Abstract

Density-based wave function analysis enables unambiguous comparisons of electronic structure computed by different methods and removes ambiguity of orbital choices. Here, we use this tool to investigate the performance of different spin-flip methods for several prototypical diradicals and triradicals. In contrast to previous calibration studies that focused on energy gaps between high and low spin-states, we focus on the properties of the underlying wave functions, such as the number of effectively unpaired electrons. Comparison of different density functional and wave function theory results provides insight into the performance of the different methods when applied to strongly correlated systems such as polyradicals. We also show that canonical molecular orbitals for species like large copper-containing diradicals fail to correctly represent the underlying electronic structure due to highly non-Koopmans character, while density-based analysis of the same wave function delivers a clear picture of bonding pattern.

Authors:
 [1];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
  2. Ruprecht Karls Univ. of Heidelberg (Germany). Interdisciplinary Center for Scientific Computing
Publication Date:
Research Org.:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1414838
Grant/Contract Number:  
FG02-05ER15685
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 14; Journal Issue: 2; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Orms, Natalie, Rehn, Dirk, Dreuw, Andreas, and Krylov, Anna I. Characterizing bonding patterns in diradicals and triradicals by density-based wave function analysis: A uniform approach. United States: N. p., 2017. Web. doi:10.1021/acs.jctc.7b01012.
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Orms, Natalie, Rehn, Dirk, Dreuw, Andreas, & Krylov, Anna I. Characterizing bonding patterns in diradicals and triradicals by density-based wave function analysis: A uniform approach. United States. https://doi.org/10.1021/acs.jctc.7b01012
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Orms, Natalie, Rehn, Dirk, Dreuw, Andreas, and Krylov, Anna I. Thu . "Characterizing bonding patterns in diradicals and triradicals by density-based wave function analysis: A uniform approach". United States. https://doi.org/10.1021/acs.jctc.7b01012. https://www.osti.gov/servlets/purl/1414838.
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@article{osti_1414838,
title = {Characterizing bonding patterns in diradicals and triradicals by density-based wave function analysis: A uniform approach},
author = {Orms, Natalie and Rehn, Dirk and Dreuw, Andreas and Krylov, Anna I.},
abstractNote = {Density-based wave function analysis enables unambiguous comparisons of electronic structure computed by different methods and removes ambiguity of orbital choices. Here, we use this tool to investigate the performance of different spin-flip methods for several prototypical diradicals and triradicals. In contrast to previous calibration studies that focused on energy gaps between high and low spin-states, we focus on the properties of the underlying wave functions, such as the number of effectively unpaired electrons. Comparison of different density functional and wave function theory results provides insight into the performance of the different methods when applied to strongly correlated systems such as polyradicals. We also show that canonical molecular orbitals for species like large copper-containing diradicals fail to correctly represent the underlying electronic structure due to highly non-Koopmans character, while density-based analysis of the same wave function delivers a clear picture of bonding pattern.},
doi = {10.1021/acs.jctc.7b01012},
journal = {Journal of Chemical Theory and Computation},
number = 2,
volume = 14,
place = {United States},
year = {Thu Dec 21 00:00:00 EST 2017},
month = {Thu Dec 21 00:00:00 EST 2017}
}
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https://doi.org/10.1021/acs.jctc.7b01012
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