TY - JOUR
T1 - Interpretation and Automatic Generation of Fermi-Orbital Descriptors
AU - Schwalbe, Sebastian
AU - Trepte, Kai
AU - Fiedler, Lenz
AU - Johnson, Alex I.
AU - Kraus, Jakob
AU - Hahn, Torsten
AU - Peralta, Juan E.
AU - Jackson, Koblar A.
AU - Kortus, Jens
N1 - Funding Information:
S. Schwalbe and K. Trepte designed the work and wrote the first draft. S. Schwalbe coded all python based generators, while the fodMC was coded by K. Trepte. The other authors contributed ideas for the code development, code testing, discussions, and revisions. The authors thank the ZIH in Dresden for computational time. K. Trepte, A. I. Johnson, J. E. Peralta and K. A. Jackson are supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, as part of the Computational Chemical Sciences Program under Award Number #DE-SC0018331. J. Kortus thanks the German Research Foundation (DFG) for financial support of this study KO 1924/9-1. The authors are grateful to our referees for their useful comments, which have increased the scientific content and quality of the manuscript. Furthermore, we would like to thank Mark R. Pederson for creating the FLO-SIC method, an achievement that has initialized our interest in the topic and started this work.
Publisher Copyright:
© 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.
PY - 2019/12/15
Y1 - 2019/12/15
N2 - We present an interpretation of Fermi-orbital descriptors (FODs) and argue that these descriptors carry chemical bonding information. We show that a bond order derived from these FODs agrees well with reference values, and highlight that optimized FOD positions used within the Fermi-Löwdin orbital self-interaction correction (FLO-SIC) method correspond to expectations from Linnett's double-quartet theory, which is an extension of Lewis theory. This observation is independent of the underlying exchange-correlation functional, which is shown using the local spin density approximation, the Perdew–Burke–Ernzerhof generalized gradient approximation (GGA), and the strongly constrained and appropriately normed meta-GGA. To make FOD positions generally accessible, we propose and discuss four independent methods for the generation of Fermi-orbital descriptors, their implementation as well as their advantages and drawbacks. In particular, we introduce a re-implementation of the electron force field, an approach based on the centers of mass of orbital densities, a Monte Carlo-based algorithm, and a method based on Lewis-like bonding information. All results are summarized with respect to future developments of FLO-SIC and related methods.
AB - We present an interpretation of Fermi-orbital descriptors (FODs) and argue that these descriptors carry chemical bonding information. We show that a bond order derived from these FODs agrees well with reference values, and highlight that optimized FOD positions used within the Fermi-Löwdin orbital self-interaction correction (FLO-SIC) method correspond to expectations from Linnett's double-quartet theory, which is an extension of Lewis theory. This observation is independent of the underlying exchange-correlation functional, which is shown using the local spin density approximation, the Perdew–Burke–Ernzerhof generalized gradient approximation (GGA), and the strongly constrained and appropriately normed meta-GGA. To make FOD positions generally accessible, we propose and discuss four independent methods for the generation of Fermi-orbital descriptors, their implementation as well as their advantages and drawbacks. In particular, we introduce a re-implementation of the electron force field, an approach based on the centers of mass of orbital densities, a Monte Carlo-based algorithm, and a method based on Lewis-like bonding information. All results are summarized with respect to future developments of FLO-SIC and related methods.
KW - FLO-SIC
KW - Linnett double-quartet theory
KW - chemical bonding
KW - density functional theory
UR - http://www.scopus.com/inward/record.url?scp=85072227633&partnerID=8YFLogxK
U2 - 10.1002/jcc.26062
DO - 10.1002/jcc.26062
M3 - Article
C2 - 31503364
AN - SCOPUS:85072227633
VL - 40
SP - 2843
EP - 2857
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 32
ER -