Self-Interaction Corrections Within the Fermi-Orbital-Based Formalism

Pederson, Mark R.; Baruah, Tunna

doi:10.1016/bs.aamop.2015.06.005

Cited by 52 publications

(47 citation statements)

References 59 publications

(77 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It was for example very successful to use the Fermi an indication of the larger Coulomb repulsion from the additional core electrons. The out of plane Fermi-Orbital positions in the systems with six-membered carbon rings have also been reported by Pederson and Baruah in applications to Benzene [48] In some cases we even obtain a more realistic level ordering from the FOSIC calculation than from LDA. One representative example is given in Fig.…”

Section: Resultssupporting

confidence: 79%

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

Hahn

Liebing

Kortus

et al. 2015

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

The correction of the self-interaction error (SIE) that is inherent to all standard density functional theory (DFT) calculations is an object of increasing interest. In this article we apply the very recently developed Fermi-orbital based approach for the self-interaction correction (FOSIC) [1,2] to a set of different molecular systems. Our study covers systems ranging from simple diatomic to large organic molecules. We focus our analysis on the direct estimation of the ionization potential from orbital eigenvalues.

show abstract

Section: Resultssupporting

confidence: 79%

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

Hahn

Liebing

Kortus

et al. 2015

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

show abstract

“…In the present study, we compute the orbitals using the concept of the Fermi hole 9 to build spatially localized Fermi orbitals in one step. These orbitals are characterized by Fermi-orbital descriptors 10 (FODs) that can be interpreted as quasi-classical positions of electrons. These localized orbitals are then symmetrically orthonormalized using a Löwdin orthogonalization approach.…”

Section: Introductionmentioning

confidence: 99%

Fractional Occupation Numbers and Self-Interaction Correction-Scaling Methods with the Fermi-Lowdin Orbital Self-Interaction Correction Approach

Aquino¹,

Shinde²,

Wong³

2020

Preprint

View full text Add to dashboard Cite

We derive an alternate expression for the Fermi-Lowdin Orbital Self-Interaction Correction (FLO-SIC) energy gradient and re-visit how the FLO-SIC methodology can be seen as a constrained unitary transformation acting on canonical Kohn-Sham orbitals. We present a new performance and accuracy analysis of the FLO-SIC approach, which we have recently implemented in the massively-parallelized NWChem quantum chemistry software package. Our FLO-SIC implementation has been tested for the prediction of total energies, atomization energies, and ionization potentials of small molecules and relatively large aromatic systems. The ionization potentials of multi-electron systems are calculated with the adaptation of fractional occupation numbers within FLO-SIC. We also carefully examine the possible improvements of these predictions with various SIC scaling methods based on kinetic energy densities and gradients of electronic densities.

show abstract

“…Shortly thereafter, the Wisconsin SIC group [33][34][35] suggested the use of localization-equations as a variational means for addressing the unitary non-invariance that existed in the original formulation. This approach has been the primary means for variational self-interaction corrections as discussed in recent reviews [36][37][38][39][40][41][42][43]. While the original version of SIC [33][34][35] only considered real orbitals, several researchers [40,44,45] have noted that there is no a priori reason to expect that complex orbitals could not lead to lower SIC energies and have derived additional formulae for their minimization.…”

Section: Fermi-löwdin Orbitals For Unitarily Invariant Sicmentioning

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%

See 1 more Smart Citation

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

et al. 2017

Self Cite

View full text Add to dashboard Cite

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).

show abstract

Self-Interaction Corrections Within the Fermi-Orbital-Based Formalism

Cited by 52 publications

References 59 publications

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

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

Fractional Occupation Numbers and Self-Interaction Correction-Scaling Methods with the Fermi-Lowdin Orbital Self-Interaction Correction Approach

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

Contact Info

Product

Resources

About