The rise and fall of stretched bond errors: Extending the analysis of Perdew-Zunger self-interaction corrections of reaction barrier heights beyond the LSDA.

Incorporating self-interaction corrections (SIC) significantly improves chemical reaction barrier height predictions made using density functional theory methods. We present a detailed orbital-by-orbital analysis of these corrections for three semi-local density functional approximations (DFAs) situated on the three lowest rungs of Jacob's ladder of approximations. The analysis is based on Fermi-Löwdin Orbital Self-Interaction Correction (FLOSIC) calculations performed at several steps along the reaction pathway from the reactants (R) to the transition state (TS) to the products (P) for four representative reactions selected from the BH76 benchmark set. For all three functionals, the major contribution to self-interaction corrections of the barrier heights can be traced to stretched bond orbitals that develop near the TS configuration. The magnitude of the ratio of the self-exchange-correlation energy to the self-Hartree energy (XC/H) for a given orbital is introduced as an indicator of one-electron self-interaction error. XC/H = 1.0 implies that an orbital's self-exchange-correlation energy exactly cancels its self-Hartree energy and that the orbital, therefore, makes no contribution to the SIC in the FLOSIC scheme. For the practical DFAs studied here, XC/H spans a range of values. The largest values are obtained for stretched or strongly lobed orbitals. We show that significant differences in XC/H for corresponding orbitals in the R, TS, and P configurations can be used to identify the major contributors to the SIC of barrier heights and reaction energies. Based on such comparisons, we suggest that barrier height predictions made using the strongly constrained and appropriately normed meta-generalized gradient approximation may have attained the best accuracy possible for a semi-local functional using the Perdew-Zunger SIC approach.

Bond length alternation of π-conjugated polymers predicted by the Fermi-Löwdin orbital self-interaction correction method.

π-conjugated polymers have been used in a wide range of practical applications, partly due to their unique properties that originate in the delocalization of electrons through the polymer backbone. The level of delocalization can be characterized by the induced bond length alternation (BLA), with shorter BLA connected with strong delocalization and vice versa. The accurate description of this structural parameter can be considered a benchmark for testing the capability of different electronic structure methods for self-interaction error (SIE) removal and electron correlation inclusion. Density functional theory (DFT), in its local or semi-local flavors, suffers from SIE and, thus, underestimates the BLA compared to self-interaction-free methods. In this work, we utilize the Fermi-Löwdin orbital self-interaction correction (FLOSIC) method for one-electron self-interaction removal to characterize the BLA of five oligomers with increasing length extrapolated to the polymeric limit. We compare the self-interaction-free BLA to several DFT approximations, Møller-Plesset second-order perturbation theory (MP2), and the BLA obtained with the domain based local pair natural orbital CCSD(T) [DLPNO-CCSD(T)] approximation. Our findings show that FLOSIC corrects for the small BLA given by (semi-)local DFT approximations, but it tends to overcorrect with respect to CAM-B3LYP, MP2, and DLPNO-CCSD(T).

Use of FLOSIC for understanding anion-solvent interactions.

An Achille's heel of lower-rung density-functional approximations is that the highest-occupied-molecular-orbital energy levels of anions, known to be stable or metastable in nature, are often found to be positive in the worst case or above the lowest-unoccupied-molecular-orbital levels on neighboring complexes that are not expected to accept charge. A trianionic example, [Cr(C2O4)3]3-, is of interest for constraining models linking Cr isotope ratios in rock samples to oxygen levels in Earth's atmosphere over geological timescales. Here we describe how crowd sourcing can be used to carry out self-consistent Fermi-Löwdin-Orbital-Self-Interaction corrected calculations (FLOSIC) on this trianion in solution. The calculations give a physically correct description of the electronic structure of the trianion and water. In contrast, uncorrected local density approximation (LDA) calculations result in approximately half of the anion charge being transferred to the water bath due to the effects of self-interaction error. Use of group-theory and the intrinsic sparsity of the theory enables calculations roughly 125 times faster than our initial implementation in the large N limit reached here. By integrating charge density densities and Coulomb potentials over regions of space and analyzing core-level shifts of the Cr and O atoms as a function of position and functional, we unambiguously show that FLOSIC, relative to LDA, reverses incorrect solute-solvent charge transfer in the trianion-water complex. In comparison to other functionals investigated herein, including Hartree-Fock and the local density approximation, the FLOSIC Cr 1s eigenvalues provide the best agreement with experimental core ionization energies.

Downward quantum learning from element 118: Automated generation of Fermi-Löwdin orbitals for all atoms.

A new algorithm based on a rigorous theorem and quantum data computationally mined from element 118 guarantees automated construction of initial Fermi-Löwdin-Orbital (FLO) starting points for all elements in the Periodic Table. It defines a means for constructing a small library of scalable FLOs for universal use in molecular and solid-state calculations. The method can be systematically improved for greater efficiency and for applications to excited states such as x-ray excitations and optically silent excitations. FLOs were introduced to recast the Perdew-Zunger self-interaction correction (PZSIC) into an explicit unitarily invariant form. The FLOs are generated from a set of N quasi-classical electron positions, referred to as Fermi-Orbital descriptors (FODs), and a set of N-orthonormal single-electron orbitals. FOD positions, when optimized, minimize the PZSIC total energy. However, creating sets of starting FODs that lead to a positive definite Fermi orbital overlap matrix has proven to be challenging for systems composed of open-shell atoms and ions. The proof herein guarantees the existence of a FLOSIC solution and further guarantees that if a solution for N electrons is found, it can be used to generate a minimum of N - 1 and a maximum of 2N - 2 initial starting points for systems composed of a smaller number of electrons. Applications to heavy and super-heavy atoms are presented. All starting solutions reported here were obtained from a solution for element 118, Oganesson.

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

Density functional theory (DFT) suffers from self-interaction 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 self-interaction 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-by-orbital correction scheme to remove the one-electron SIE. In the context of barrier heights, this allows an analysis of how the self-interaction correction (SIC) for each orbital contributes to the calculated barriers using Fermi-Löwdin 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 ΔETotalSIC ≈ ΔEPOSIC, where ΔETotalSIC 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.

Spin-crossover complexes: Self-interaction correction vs density correction.

Complexes containing a transition metal atom with a 3d4-3d7 electron configuration typically have two low-lying, high-spin (HS) and low-spin (LS) states. The adiabatic energy difference between these states, known as the spin-crossover energy, is small enough to pose a challenge even for electronic structure methods that are well known for their accuracy and reliability. In this work, we analyze the quality of electronic structure approximations for spin-crossover energies of iron complexes with four different ligands by comparing energies from self-consistent and post-self-consistent calculations for methods based on the random phase approximation and the Fermi-Löwdin self-interaction correction. Considering that Hartree-Fock densities were found by Song et al., J. Chem. Theory Comput. 14, 2304 (2018), to eliminate the density error to a large extent, and that the Hartree-Fock method and the Perdew-Zunger-type self-interaction correction share some physics, we compare the densities obtained with these methods to learn their resemblance. We find that evaluating non-empirical exchange-correlation energy functionals on the corresponding self-interaction-corrected densities can mitigate the strong density errors and improves the accuracy of the adiabatic energy differences between HS and LS states.

Complex Fermi-Löwdin orbital self-interaction correction.

This paper introduces the use of complex Fermi orbital descriptors (FODs) in the Fermi-Löwdin self-interaction-corrected density functional theory (FLOSIC). With complex FODs, the Fermi-Löwdin orbitals (FLOs) that are used to evaluate the SIC correction to the total energy become complex. Complex FLO-SIC (cFLOSIC) calculations based on the local spin density approximation produce total energies that are generally lower than the corresponding energies found with FLOSIC restricted to real orbitals (rFLOSIC). The cFLOSIC results are qualitatively similar to earlier Perdew-Zunger SIC (PZ-SIC) calculations using complex orbitals [J. Chem. Phys. 80, 1972 (1984); Phys. Rev. A 84, 050501(R) (2011); and J. Chem. Phys. 137, 124102 (2012)]. The energy lowering stems from the exchange-correlation part of the self-interaction correction. The Hartree part of the correction is more negative in rFLOSIC. The energy difference between real and complex solutions is greater for more strongly hybridized FLOs in atoms and for FLOs corresponding to double and triple bonds in molecules. The case of N2 is examined in detail to show the differences between the real and complex FLOs. We show that the complex triple-bond orbitals are simple, and physically appealing combinations of π and σg orbitals that have not been discussed before. Consideration of complex FODs, and resulting unitary transformations, underscores the fact that FLO centroids are not necessarily good guesses for FOD positions in a FLOSIC calculation.

Fermi-Löwdin orbital self-interaction correction of adsorption energies on transition metal ions.

Density functional theory (DFT)-based descriptions of the adsorption of small molecules on transition metal ions are prone to self-interaction errors. Here, we show that such errors lead to a large over-estimation of adsorption energies of small molecules on Cu+, Zn+, Zn2+, and Mn+ in local spin density approximation (LSDA) and Perdew, Burke, Ernzerhof (PBE) generalized gradient approximation calculations compared to reference values computed using the coupled-cluster with single, doubles, and perturbative triple excitations method. These errors are significantly reduced by removing self-interaction using the Perdew-Zunger self-interaction correction (PZ-SIC) in the Fermi-Löwdin Orbital (FLO) SIC framework. In the case of FLO-PBE, typical errors are reduced to less than 0.1 eV. Analysis of the results using DFT energies evaluated on self-interaction-corrected densities [DFT(@FLO)] indicates that the density-driven contributions to the FLO-DFT adsorption energy corrections are roughly the same size in DFT = LSDA and PBE, but the total corrections due to removing self-interaction are larger in LSDA.

Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods.

We study the effect of self-interaction errors on the barrier heights of chemical reactions. For this purpose, we use the well-known Perdew-Zunger self-interaction-correction (PZSIC) [J. P. Perdew and A. Zunger, Phys. Rev. B 23, 5048 (1981)] as well as two variations of the recently developed, locally scaled self-interaction correction (LSIC) [Zope et al., J. Chem. Phys. 151, 214108 (2019)] to study the barrier heights of the BH76 benchmark dataset. Our results show that both PZSIC and especially the LSIC methods improve the barrier heights relative to the local density approximation (LDA). The version of LSIC that uses the iso-orbital indicator z as a scaling factor gives a more consistent improvement than an alternative version that uses an orbital-dependent factor w based on the ratio of orbital densities to the total electron density. We show that LDA energies evaluated using the self-consistent and self-interaction-free PZSIC densities can be used to assess density-driven errors. The LDA reaction barrier errors for the BH76 set are found to contain significant density-driven errors for all types of reactions contained in the set, but the corrections due to adding SIC to the functional are much larger than those stemming from the density for the hydrogen transfer reactions and of roughly equal size for the non-hydrogen transfer reactions.

How well do self-interaction corrections repair the overestimation of static polarizabilities in density functional calculations?

We examine the effect of removing self-interaction error (SIE) on the calculation of molecular polarizabilities in the local spin density (LSDA) and generalized gradient approximations (GGA). To this end, we utilize a database of 132 molecules taken from a recent benchmark study [Hait and Head-Gordon, Phys. Chem. Chem. Phys., 2018, 20, 19800] to assess the influence of SIE on polarizabilities by comparing results with accurate reference data. Our results confirm that the general overestimation of molecular polarizabilities by these density functional approximations can be attributed to SIE. However, removing SIE using the Perdew-Zunger self-interaction-correction (PZ-SIC) method, implemented using the Fermi-Löwdin Orbital SIC approach, leads to an underestimation of molecular polarizabilities, showing that PZ-SIC overcorrects when combined with LSDA or GGA. Application of a recently proposed locally scaled SIC [Zope, et al., J. Chem. Phys., 2019, 151, 214108] is found to provide more accurate polarizabilities. We attribute this to the ability of the local scaling scheme to selectively correct for SIE in the regions of space where the correction is needed most.

Self-interaction correction in water-ion clusters.

We study the importance of self-interaction errors in density functional approximations for various water-ion clusters. We have employed the Fermi-Löwdin orbital self-interaction correction (FLOSIC) method in conjunction with the local spin-density approximation, Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA), and strongly constrained and appropriately normed (SCAN) meta-GGA to describe binding energies of hydrogen-bonded water-ion clusters, i.e., water-hydronium, water-hydroxide, water-halide, and non-hydrogen-bonded water-alkali clusters. In the hydrogen-bonded water-ion clusters, the building blocks are linked by hydrogen atoms, although the links are much stronger and longer-ranged than the normal hydrogen bonds between water molecules because the monopole on the ion interacts with both permanent and induced dipoles on the water molecules. We find that self-interaction errors overbind the hydrogen-bonded water-ion clusters and that FLOSIC reduces the error and brings the binding energies into closer agreement with higher-level calculations. The non-hydrogen-bonded water-alkali clusters are not significantly affected by self-interaction errors. Self-interaction corrected PBE predicts the lowest mean unsigned error in binding energies (≤50 meV/H2O) for hydrogen-bonded water-ion clusters. Self-interaction errors are also largely dependent on the cluster size, and FLOSIC does not accurately capture the subtle variation in all clusters, indicating the need for further refinement.

Exploring and enhancing the accuracy of interior-scaled Perdew-Zunger self-interaction correction.

The Perdew-Zunger self-interaction correction (PZ-SIC) improves the performance of density functional approximations for the properties that involve significant self-interaction error (SIE), as in stretched bond situations, but overcorrects for equilibrium properties where SIE is insignificant. This overcorrection is often reduced by local scaling self-interaction correction (LSIC) of the PZ-SIC to the local spin density approximation (LSDA). Here, we propose a new scaling factor to use in an LSIC-like approach that satisfies an additional important constraint: the correct coefficient of the atomic number Z in the asymptotic expansion of the exchange-correlation (xc) energy for atoms. LSIC and LSIC+ are scaled by functions of the iso-orbital indicator zσ, which distinguishes one-electron regions from many-electron regions. LSIC+ applied to the LSDA works better for many equilibrium properties than LSDA-LSIC and the Perdew, Burke, and Ernzerhof generalized gradient approximation (GGA), and almost close to the strongly constrained and appropriately normed (SCAN) meta-GGA. LSDA-LSIC and LSDA-LSIC+, however, fail to predict interaction energies involving weaker bonds, in sharp contrast to their earlier successes. It is found that more than one set of localized SIC orbitals can yield a nearly degenerate energetic description of the same multiple covalent bond, suggesting that a consistent chemical interpretation of the localized orbitals requires a new way to choose their Fermi orbital descriptors. To make a locally scaled down SIC to functionals beyond the LSDA requires a gauge transformation of the functional's energy density. The resulting SCAN-sdSIC, evaluated on SCAN-SIC total and localized orbital densities, leads to an acceptable description of many equilibrium properties including the dissociation energies of weak bonds.

Density-related properties from self-interaction corrected density functional theory calculations.

The Perdew-Zunger self-interaction correction (PZ-SIC) removes unphysical electron self-interaction from calculations employing standard density functional approximations. Doing so improves many computed properties, bringing them into better agreement with experimental observations or with results from high-level quantum chemistry calculations. However, while PZ-SIC generally corrects in the right direction relative to the corresponding reference values, in many cases, it over-corrects. For this reason, scaled-down versions of PZ-SIC have been proposed and investigated. These approaches have mostly employed exterior scaling in which SIC correction terms are scaled in the same way at every point in space. Recently, a new local, or interior, scaling SIC method was proposed on non-empirical grounds to restore a property of the exact, but unknown, density functional that is broken in PZ-SIC. In this approach, the scaling at each point depends on the character of the charge density at that point. However, the local scaling can be done in various ways while still restoring the behavior of the exact functional. In this work, we compare and contrast the performance of various interior scaling approaches for addressing over-corrections of calculated molecular dipole moments and atomic polarizabilities and properties that reflect the nature of the electronic charge density.

The Fermi-Löwdin self-interaction correction for ionization energies of organic molecules.

(Semi)-local density functional approximations (DFAs) suffer from self-interaction error (SIE). When the first ionization energy (IE) is computed as the negative of the highest-occupied orbital (HO) eigenvalue, DFAs notoriously underestimate them compared to quasi-particle calculations. The inaccuracy for the HO is attributed to SIE inherent in DFAs. We assessed the IE based on Perdew-Zunger self-interaction correction on 14 small to moderate-sized organic molecules relevant in organic electronics and polymer donor materials. Although self-interaction corrected DFAs were found to significantly improve the IE relative to the uncorrected DFAs, they overestimate. However, when the self-interaction correction is interiorly scaled using a function of the iso-orbital indicator zσ, only the regions where SIE is significant get a correction. We discuss these approaches and show how these methods significantly improve the description of the HO eigenvalue for the organic molecules.

Study of self-interaction errors in density functional predictions of dipole polarizabilities and ionization energies of water clusters using Perdew-Zunger and locally scaled self-interaction corrected methods.

We studied the effect of self-interaction error (SIE) on the static dipole polarizabilities of water clusters modeled with three increasingly sophisticated, non-empirical density functional approximations (DFAs), viz., the local spin density approximation (LDA), the Perdew-Burke-Ernzerhof (PBE) generalized-gradient approximation (GGA), and the strongly constrained and appropriately normed (SCAN) meta-GGA, using the Perdew-Zunger self-interaction-correction (PZ-SIC) energy functional in the Fermi-Löwdin orbital SIC framework. Our results show that while all three DFAs overestimate the cluster polarizabilities, the description systematically improves from LDA to PBE to SCAN. The self-correlation free SCAN predicts polarizabilities quite accurately with a mean absolute error (MAE) of 0.53 bohr3 with respect to coupled cluster singles and doubles (CCSD) values. Removing SIE using PZ-SIC correctly reduces the DFA polarizabilities, but overcorrects, resulting in underestimated polarizabilities in SIC-LDA, SIC-PBE, and SIC-SCAN. Finally, we applied a recently proposed locally scaled SIC (LSIC) method using a quasi self-consistent scheme and using the kinetic energy density ratio as an iso-orbital indicator. The results show that the LSIC polarizabilities are in excellent agreement with mean absolute errors of 0.08 bohr3 for LSIC-LDA and 0.06 bohr3 for LSIC-PBE with most recent CCSD polarizabilities. Likewise, the ionization energy estimates as absolute of highest occupied energy eigenvalue predicted by LSIC are also in excellent agreement with CCSD(T) ionization energies with MAEs of 0.4 eV for LSIC-LDA and 0.06 eV for LSIC-PBE. The LSIC-LDA predictions of ionization energies are comparable to the reported GW ionization energies, while the LSIC-PBE ionization energies are more accurate than the reported GW results.

Application of Self-Interaction Corrected Density Functional Theory to Early, Middle, and Late Transition States.

Density functional theory (DFT)-based methods often significantly underpredict chemical reaction barriers compared with experiments because of the tendency of DFT to overstabilize transition states with stretched bonds due to the impact of unphysical electron self-interaction. However, many reactions have early or late transition states where the transition state geometry closely resembles the reactants or products, respectively. The role of self-interaction in those cases is not known. Here we compare the performance of DFT with and without self-interaction correction (SIC) for describing the hydrogenation of CO and CO2 catalyzed by a Lewis acid-base pair incorporated onto an aromatic cluster, using CCSD(T) results for reference. The three elementary steps in these reactions consist of an early, a middle, and a late transition. Our results show that the Perdew-Zunger SIC (PZ-SIC), implemented in the Fermi-Löwdin orbital SIC (FLO-SIC) approach, qualitatively improves the description of the forward and reverse reaction barriers relative to uncorrected DFT for the middle transition but not the early or late transitions. By contrast, the local scaling SIC (LSIC) method, also implemented in the FLO-SIC framework, significantly improves the calculated barriers over DFT and PZ-SIC in all but one case. The results also show how the FLO-SIC approach can provide insight into the bonding in aromatic systems.

A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction. II. Gauge consistency of the energy density at three levels of approximation.

The Perdew-Zunger (PZ) self-interaction correction (SIC) was designed to correct the one-electron limit of any approximate density functional for the exchange-correlation (xc) energy, while yielding no correction to the exact functional. Unfortunately, it spoils the slowly varying (in space) limits of the uncorrected approximate functionals, where those functionals are right by construction. The right limits can be restored by locally scaling down the energy density of the PZ SIC in many-electron regions, but then a spurious correction to the exact functional would be found unless the self-Hartree and exact self-xc terms of the PZ SIC energy density were expressed in the same gauge. Only the local density approximation satisfies the same-gauge condition for the energy density, which explains why the recent local-scaling SIC is found here to work excellently for atoms and molecules only with this basic approximation and not with the more advanced generalized gradient approximations (GGAs) and meta-GGAs, which lose the Hartree gauge via simplifying integrations by parts. The transformation of energy density that achieves the Hartree gauge for the exact xc functional can also be applied to approximate functionals. Doing so leads to a simple scaled-down self-interaction correction that is typically much more accurate than PZ SIC in tests for many molecular properties (including equilibrium bond lengths). The present work unambiguously shows that the largest errors of PZ SIC applied to standard functionals at three levels of approximation can be removed by restoring their correct slowly varying density limits. It also confirms the relevance of these limits to atoms and molecules.

Self-interaction error overbinds water clusters but cancels in structural energy differences.

We gauge the importance of self-interaction errors in density functional approximations (DFAs) for the case of water clusters. To this end, we used the Fermi-Löwdin orbital self-interaction correction method (FLOSIC) to calculate the binding energy of clusters of up to eight water molecules. Three representative DFAs of the local, generalized gradient, and metageneralized gradient families [i.e., local density approximation (LDA), Perdew-Burke-Ernzerhof (PBE), and strongly constrained and appropriately normed (SCAN)] were used. We find that the overbinding of the water clusters in these approximations is not a density-driven error. We show that, while removing self-interaction error does not alter the energetic ordering of the different water isomers with respect to the uncorrected DFAs, the resulting binding energies are corrected toward accurate reference values from higher-level calculations. In particular, self-interaction-corrected SCAN not only retains the correct energetic ordering for water hexamers but also reduces the mean error in the hexamer binding energies to less than 14 meV/[Formula: see text] from about 42 meV/[Formula: see text] for SCAN. By decomposing the total binding energy into many-body components, we find that large errors in the two-body interaction in SCAN are significantly reduced by self-interaction corrections. Higher-order many-body errors are small in both SCAN and self-interaction-corrected SCAN. These results indicate that orbital-by-orbital removal of self-interaction combined with a proper DFA can lead to improved descriptions of water complexes.

Importance of self-interaction-error removal in density functional calculations on water cluster anions.

Accurate description of the excess charge in water cluster anions is challenging for standard semi-local and (global) hybrid density functional approximations (DFAs). Using the recent unitary invariant implementation of the Perdew-Zunger self-interaction correction (SIC) method using Fermi-Löwdin orbitals, we assess the effect of self-interaction error on the vertical detachment energies of water cluster anions with the local spin density approximation (LSDA), Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation, and the strongly constrained and appropriately normed (SCAN) meta-GGA functionals. Our results show that for the relative energies of isomers with respect to reference CCSD(T) values, the uncorrected SCAN functional has the smallest deviation of 21 meV, better than that for the MP2 method. The performance of SIC-SCAN is comparable to that of MP2 and is better than SIC-LSDA and SIC-PBE, but it reverses the ordering of the two lowest isomers for water hexamer anions. Removing self interaction error (SIE) corrects the tendency of LSDA, PBE, and SCAN to over-bind the extra electron. The vertical detachment energies (VDEs) of water cluster anions, obtained from the total energy differences of corresponding anion and neutral clusters, are significantly improved by removing self-interaction and are better than the hybrid B3LYP functional, but fall short of MP2 accuracy. Removing SIE results in substantial improvement in the position of the eigenvalue of the extra electron. The negative of the highest occupied eigenvalue after SIC provides an excellent approximation to the VDE, especially for SIC-PBE where the mean absolute error with respect to CCSD(T) is only 17 meV, the best among all approximations compared in this work.

A step in the direction of resolving the paradox of Perdew-Zunger self-interaction correction.

Self-interaction (SI) error, which results when exchange-correlation contributions to the total energy are approximated, limits the reliability of many density functional approximations. The Perdew-Zunger SI correction (PZSIC), when applied in conjunction with the local spin density approximation (LSDA), improves the description of many properties, but overall, this improvement is limited. Here, we propose a modification to PZSIC that uses an iso-orbital indicator to identify regions where local SICs should be applied. Using this local-scaling SIC (LSIC) approach with LSDA, we analyze predictions for a wide range of properties including, for atoms, total energies, ionization potentials, and electron affinities and, for molecules, atomization energies, dissociation energy curves, reaction energies, and reaction barrier heights. LSIC preserves the results of PZSIC-LSDA for properties where it is successful and provides dramatic improvements for many of the other properties studied. Atomization energies calculated using LSIC are better than those of the Perdew, Burke, and Ernzerhof generalized gradient approximation (GGA) and close to those obtained with the strongly constrained and appropriately normed meta-GGA. LSIC also restores the uniform gas limit for the exchange energy that is lost in PZSIC-LSDA. Further performance improvements may be obtained by an appropriate combination or modification of the local scaling factor and the particular density functional approximation.