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Fractional occupation numbers and self-interaction correction-scaling methods with the Fermi-Löwdin orbital self-interaction correction approach

Journal Article · · Journal of Computational Chemistry
DOI:https://doi.org/10.1002/jcc.26168· OSTI ID:1818301
 [1];  [2];  [2]
  1. Univ. of California, Riverside, CA (United States); University of California, Riverside
  2. Univ. of California, Riverside, CA (United States)
+ Show Author Affiliations
In this work, we present a new assessment of the Fermi-Löwdin orbital self-interaction correction (FLO-SIC) approach with an emphasis on its performance for predicting energies as a function of fractional occupation numbers (FONs) for various multielectron systems. Our approach is implemented in the massively parallelized NWChem quantum chemistry software package and has been benchmarked on the prediction of total energies, atomization energies, and ionization potentials of small molecules and relatively large aromatic systems. Within our study, we also derive an alternate expression for the FLO-SIC energy gradient expressed in terms of gradients of the Fermi-orbital eigenvalues and revisit how the FLO-SIC methodology can be seen as a constrained unitary transformation of the canonical Kohn–Sham orbitals. Finally, we conclude with calculations of energies as a function of FONs using various SIC-scaling methods to test the limits of the FLO-SIC formalism on a variety of multielectron systems. We find that these relatively simple scaling methods do improve the prediction of total energies of atomic systems as well as enhance the accuracy of energies as a function of FONs for other multielectron chemical species.
Research Organization:
Univ. of California, Riverside, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0016269
OSTI ID:
1818301
Alternate ID(s):
OSTI ID: 1802903
OSTI ID: 1598921
Journal Information:
Journal of Computational Chemistry, Journal Name: Journal of Computational Chemistry Journal Issue: 12 Vol. 41; ISSN 0192-8651
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

fractional occupation number
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Fermi-Lowdin orbitals
density functional theory
ionization potential
self-interaction correction