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This content will become publicly available on December 21, 2018

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

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]
  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:
Grant/Contract Number:
FG02-05ER15685
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Name: Journal of Chemical Theory and Computation; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Research Org:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1414838