Study of Self-Interaction Errors in Density Functional Calculations of Magnetic Exchange Coupling Constants Using Three Self-Interaction Correction Methods

Mishra, Prakash; Yamamoto, Yoh; Chang, Po-Hao; Nguyen, Duyen B.; Peralta, Juan E.; Baruah, Tunna; Zope, Rajendra R.

doi:10.1021/acs.jpca.1c10354

Cited by 6 publications

(3 citation statements)

References 111 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Additionally, a SIC method may perform poorly with the organic ligands of MCTM systems due to an over-correction of errors. Some promising results for an MCTM ([Cu 2 Cl 6 ] 2– ) were shown in a recent study with a locally scaled application of SIC . Thus, it is important to understand the accuracy and overall tendencies of XC functionals prior to any error-correction or additional calculations.…”

Section: Functionals Of the Studymentioning

confidence: 99%

Comparative Density Functional Theory Study of Magnetic Exchange Couplings in Dinuclear Transition-Metal Complexes

Fitzhugh

Furness

Pederson

et al. 2023

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

Multicenter transition-metal complexes (MCTMs) with magnetically interacting ions have been proposed as components for information-processing devices and storage units. For any practical application of MCTMs as magnetic units, it is crucial to characterize their magnetic behavior, and in particular, the isotropic magnetic exchange coupling, J, between its magnetic centers. Due to the large size of typical MCTMs, density functional theory is the only practical electronic structure method for evaluating the J coupling. Here, we assess the accuracy of different density functional approximations for predicting the magnetic couplings of eight dinuclear transition-metal complexes, including five dimanganese, two dicopper, and one divanadium with known reliable experimental J couplings spanning from ferromagnetic to strong antiferromagnetic. The density functionals considered include global hybrid functionals which mix semilocal density functional approximations and exact exchange with a fixed admixing parameter, six local hybrid functionals where the admixing parameters are extended to be spatially dependent, the SCAN and r 2 SCAN meta-generalized gradient approximations (GGAs), and two widely used GGAs. We found that global hybrids tested in this work have a tendency to over-correct the error in magnetic coupling parameters from the Perdew−Burke−Ernzerhof (PBE) GGA as seen for manganese complexes. The performance of local hybrid density functionals shows no improvement in terms of bias and is scattered without a clear trend, suggesting that more efforts are needed for the extension from global to local hybrid density functionals for this particular property. The SCAN and r 2 SCAN meta-GGAs are found to perform as well as benchmark global hybrids on most tested complexes.We further analyze the charge density redistribution of meta-GGAs as well as global and local hybrid density functionals with respect to that of PBE, in connection to the self-interaction error or delocalization error.

show abstract

Section: Functionals Of the Studymentioning

confidence: 99%

Comparative Density Functional Theory Study of Magnetic Exchange Couplings in Dinuclear Transition-Metal Complexes

Fitzhugh

Furness

Pederson

et al. 2023

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

show abstract

“…This leads to a failure to accurately predict properties such as electron removal energies, molecular dissociation energies, and others. 1 − 7 SIEs particularly affect the total energy of systems with stretched bonds such as the transition states (TS) of chemical reactions. 3 , 4 , 8 , 9 Standard DFAs predict an unphysical lowering of the total energy for delocalized charge distributions.…”

Section: Introductionmentioning

confidence: 99%

“…Density functional approximations (DFAs) suffer from self-interaction errors (SIEs) due to the incomplete cancellation of the self-Coulomb and self-exchange-correlation (XC) energies for one-electron densities. This leads to a failure to accurately predict properties such as electron removal energies, molecular dissociation energies, and others. − SIEs particularly affect the total energy of systems with stretched bonds such as the transition states (TS) of chemical reactions. ,,, Standard DFAs predict an unphysical lowering of the total energy for delocalized charge distributions. , In transition states, orbitals corresponding to stretched or breaking bonds can be spread over multiple atoms. For example, in the model reaction AB + C → A + BC, orbitals in the transition state may spread over all three atoms, A, B, and C, whereas the orbitals are confined to AB or C in the reactants or A or BC in the products.…”

Section: Introductionmentioning

confidence: 99%

How Do Self-Interaction Errors Associated with Stretched Bonds Affect Barrier Height Predictions?

et al. 2023

Self Cite

View full text Add to dashboard Cite

Density functional theory (DFT) suffers from selfinteraction errors (SIEs) that generally result in the underestimation of chemical reaction barrier heights. This is commonly attributed to the tendency of density functional approximations to overstabilize delocalized densities that typically occur in the stretched bonds of transition state structures. The Perdew−Zunger self-interaction correction (PZSIC) and locally scaled selfinteraction correction (LSIC) improve the prediction of barrier heights of chemical reactions, with LSIC giving better accuracy than PZSIC on average. These methods employ an orbital-byorbital correction scheme to remove the one-electron SIE. In the context of barrier heights, this allows an analysis of how the selfinteraction correction (SIC) for each orbital contributes to the calculated barriers using Fermi−Loẅdin orbitals (FLOs). We hypothesize that the SIC contribution to the reaction barrier comes mainly from a limited number of orbitals that are directly involved in bond-breaking and bond-making in the reaction transition state. We call these participant orbitals (POs), in contrast to spectator orbitals (SOs) which are not directly involved in changes to the bonding. Our hypothesis is that ΔE Total SIC ≈ ΔE PO SIC , where ΔE Total SIC is the difference in the SIC corrections for the reactants or products and the transition state. We test this hypothesis for the reaction barriers of the BH76 benchmark set of reactions. We find that the stretched-bond orbitals indeed make the largest individual SIC contributions to the barriers. These contributions increase the barrier heights relative to LSDA, which underpredicts the barrier. However, the full stretched-bond hypothesis does not hold in all cases for either PZSIC or LSIC. There are many cases where the total SIC contribution from the SOs is significant and cannot be ignored. The size of the SIC contribution to the barrier height is a key indicator. A large SIC correction is correlated to a large LSDA error in the barrier, showing that PZSIC properly gives larger corrections when corrections are needed most. A comparison of the performance of PZSIC and LSIC shows that the two methods have similar accuracy for reactions with large LSDA errors, but LSIC is clearly better for reactions with small errors. We trace this to an improved description of reaction energies in LSIC.

show abstract

Self-consistent implementation of locally scaled self-interaction-correction method

Yamamoto

Baruah

Chang

et al. 2023

The Journal of Chemical Physics

View full text Add to dashboard Cite

Recently proposed local self-interaction correction (LSIC) method [Zope, R. R. et al., J. Chem. Phys. 151, 214108 (2019)] is a one-electron self-interaction-correction (SIC) method that uses an iso-orbital indicator to apply the SIC at each point in space by scaling the exchange-correlation and Coulomb energy densities. The LSIC method is exact for the one-electron densities, also recovers the uniform electron gas limit of the uncorrected density functional approximation, and reduces to the well-known Perdew-Zunger SIC (PZSIC) method as a special case. This article presents the self-consistent implementation of the LSIC method using the ratio of Weizs ̈acker and Kohn-Sham kinetic energy densities as an iso-orbital indicator. The atomic forces as well as the forces on the Fermi-L ̈owdin orbitals are also implemented for the LSIC energy functional. Results show that LSIC with the simplest local spin density functional predicts atomization energies of AE6 dataset better than some of the most widely used GGA functional (e.g. PBE) and barrier heights of BH6 database better than some of the most widely used hybrid functionals (e.g. PBE0 and B3LYP). The LSIC method [mean absolute error (MAE) of 0.008 ̊A] predicts bond lengths of a small set of molecules better than the PZSIC-LSDA (MAE 0.042 ̊A) and LSDA (0.011 ̊A). This work shows that accurate results can be obtained from the simplest density functional by removing the self-interaction-errors using an appropriately designed SIC method.

show abstract

Study of Self-Interaction Errors in Density Functional Calculations of Magnetic Exchange Coupling Constants Using Three Self-Interaction Correction Methods

Cited by 6 publications

References 111 publications

Comparative Density Functional Theory Study of Magnetic Exchange Couplings in Dinuclear Transition-Metal Complexes

Comparative Density Functional Theory Study of Magnetic Exchange Couplings in Dinuclear Transition-Metal Complexes

How Do Self-Interaction Errors Associated with Stretched Bonds Affect Barrier Height Predictions?

Self-consistent implementation of locally scaled self-interaction-correction method

Contact Info

Product

Resources

About