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

Journal Article · · Journal of Chemical Theory and Computation
 [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
+ Show Author Affiliations

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.

Research Organization:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
FG02-05ER15685
OSTI ID:
1414838
Journal Information:
Journal of Chemical Theory and Computation, Vol. 14, Issue 2; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 36 works
Citation information provided by
Web of Science

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Cited By (9)

Improvement of the electrochemical and singlet fission properties of anthraquinones by modification of the diradical character journal January 2019
A New Class of Neutral Boron-Based Diradicals Spanned by a Two-Carbon-Atom Bridge journal January 2019
EOM-CC guide to Fock-space travel: the C 2 edition journal January 2019
Extension of frozen natural orbital approximation to open-shell references: Theory, implementation, and application to single-molecule magnets journal January 2020
Eine neue Strukturklasse neutraler borhaltiger Diradikale verbrückt über zwei Kohlenstoffatome journal January 2019
Spin-flip methods in quantum chemistry journal January 2020
Singlet–triplet energy gaps and the degree of diradical character in binuclear copper molecular magnets characterized by spin-flip density functional theory journal January 2018
Autocorrelation of electronic wave-functions: a new approach for describing the evolution of electronic structure in the course of dynamics journal May 2018
Autocorrelation of electronic wave-functions: a new approach for describing the evolution of electronic structure in the course of dynamics text January 2018

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