Fermi orbital self-interaction corrected electronic structure of molecules beyond local density approximation

Hahn, Torsten; Liebing, Simon; Kortus, Jens; Pederson, Mark R.

doi:10.1063/1.4936777

Cited by 34 publications

(37 citation statements)

References 52 publications

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“…Prior application of the FLO‐SIC method to atoms and molecules showed that there are repeating structural motifs for the FODs describing orbitals for core and valence electrons. As discussed previously, in the case of valence electrons, these structural motifs carry bonding information and are transferable between similar chemical bonding situations.…”

Section: Fermi‐orbital Descriptor Generatorsmentioning

confidence: 99%

Interpretation and Automatic Generation of Fermi‐Orbital Descriptors

et al. 2019

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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. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.

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Section: Fermi‐orbital Descriptor Generatorsmentioning

confidence: 99%

Interpretation and Automatic Generation of Fermi‐Orbital Descriptors

et al. 2019

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“…The initial FODs need to be guessed before the first SCF step. Since it is found that FODs often represent chemical bonds and lone pairs [15,25], making the initial guess is usually simple in first-and second-row elements. We calculate the forces on the FODs after the SCF loop for electronic structures as described in Ref.…”

Section: Algorithmmentioning

confidence: 99%

Full self-consistency in the Fermi-orbital self-interaction correction

2017

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The Perdew-Zunger self-interaction correction cures many common problems associated with semilocal density functionals, but suffers from a size-extensivity problem when Kohn-Sham orbitals are used in the correction. Fermi-Löwdin-orbital self-interaction correction (FLOSIC) solves the size-extensivity problem, allowing its use in periodic systems and resulting in better accuracy in finite systems. Although the previously published FLOSIC algorithm [J. Chem. Phys. 140, 121103 (2014)] appears to work well in many cases, it is not fully self-consistent. This would be particularly problematic for systems where the occupied manifold is strongly changed by the correction. In this paper we demonstrate a new algorithm for FLOSIC to achieve full self-consistency with only marginal increase of computational cost. The resulting total energies are found to be lower than previously reported non-self-consistent results.

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“…Generally speaking the best approach is to fully optimize a geometry but as discussed by Hahn et al, there may be cases where density-functional approximations yield a qualitatively incorrect geometry [32]. However, it is generally posited that the S = 2 geometry for the Fe(II)-porphyrin is bent rather than planar.…”

Section: Theoretical and Computational Detailsmentioning

confidence: 99%

“…The Löwdin symmetric reorthonormalization procedure guarantees that each localized orbital {φ iσ } is similar to its parent Fermi Orbital in a least-squares sense, but each localized orbital now depends parametrically on all the Fermi-orbital descriptors and on the spin-density matrix, or, equivalently, on the Kohn-Sham orbitals. Early indications [32,43,[47][48][49][52][53][54] are that the FLO-SIC improves orbital energies and atomization energies in a wide class of systems.…”

Section: Fermi-löwdin Orbitals For Unitarily Invariant Sicmentioning

confidence: 99%

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The Role of Self-Interaction Corrections, Vibrations, and Spin-Orbit in Determining the Ground Spin State in a Simple Heme

et al. 2017

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Without self-interaction corrections or the use of hybrid functionals, approximations to the density-functional theory (DFT) often favor intermediate spin systems over high-spin systems. In this paper, we apply the recently proposed Fermi-Löwdin-orbital self-interaction corrected density functional formalism to a simple tetra-coordinated Fe(II)-porphyrin molecule and show that the energetic orderings of the S = 1 and S = 2 spin states are changed qualitatively relative to the results of Generalized Gradient Approximation (developed by Perdew, Burke, and Ernzerhof, PBE-GGA) and Local Density Approximation (developed by Perdew and Wang, PW92-LDA). Because the energetics, associated with changes in total spin, are small, we have also calculated the second-order spin-orbit energies and the zero-point vibrational energies to determine whether such corrections could be important in metal-substituted porphins. Our results find that the size of the spin-orbit and vibrational corrections to the energy orderings are small compared to the changes due to the self-interaction correction. Spin dependencies in the Infrared (IR)/Raman spectra and the zero-field splittings are provided as a possible means for identifying the spin in porphyrins containing Fe(II).

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Fermi orbital self-interaction corrected electronic structure of molecules beyond local density approximation

Cited by 34 publications

References 52 publications

Interpretation and Automatic Generation of Fermi‐Orbital Descriptors

Interpretation and Automatic Generation of Fermi‐Orbital Descriptors

Full self-consistency in the Fermi-orbital self-interaction correction

The Role of Self-Interaction Corrections, Vibrations, and Spin-Orbit in Determining the Ground Spin State in a Simple Heme

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