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تسجيل مستخدم جديدSelf-Interaction Correction in Water-Ion Clusters
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We study the importance of self-interaction errors in density functional approximations for various water-ion clusters. We have employed the Fermi-Lowdin orbital self-interaction correction (FLOSIC) method in conjunction with LSDA, PBE, and SCAN to describe binding energies of hydrogen-bonded water-ion clusters, textit{i.e.}, water-hydronium, water-hydroxide, water-halide, as well as 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 ($leq$ 50 meV/ce{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.
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A recently proposed local self-interaction correction (LSIC) method [Zope textit{et al.} J. Chem. Phys., 2019,{bf 151}, 214108] when applied to the simplest local density approximation provides significant improvement over standard Perdew-Zunger SIC
(PZSIC) for both equilibrium properties such as total or atomization energies as well as properties involving stretched bond such as barrier heights. The method uses an iso-orbital indicator to identify the single-electron regions. To demonstrate the LSIC method, Zope textit{et al.} used the ratio $z_sigma$ of von Weizsacker $tau_sigma^W$ and total kinetic energy densities $tau_sigma$, ($z_sigma = tau_sigma^W/tau_sigma$) as a scaling factor to scale the self-interaction correction. The present work further explores the LSIC method using a simpler scaling factor as a ratio of orbital and spin densities in place of the ratio of kinetic energy densities. We compute a wide array of both, equilibrium and non-equilibrium properties using the LSIC and orbital scaling methods using this simple scaling factor and compare them with previously reported results. Our study shows that the present results with simple scaling factor are comparable to those obtained by LSIC($z_sigma$) for most properties but have slightly larger errors. We furthermore study the binding energies of small water clusters using both the scaling factors. Our results show that LSIC with $z_{sigma}$ has limitation in predicting the binding energies of weakly bonded system due to the inability of $z_{sigma}$ to distinguish weakly bonded region from slowly varying density region. LSIC when used with density ratio as a scaling factor, on the other hand, provides good description of water cluster binding energies, thus highlighting the appropriate choice of iso-orbital indicator.
We studied the effect of self-interaction error (SIE) on the static dipole polarizabilities of water clusters modelled with three increasingly sophisticated, non-empirical density functional approximations (DFAs), viz. the local spin density approxim
ation (LDA), the Perdew-Burke-Ernzherof (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-Lowdin orbital SIC (FLO-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 0.58 Bohr$^3$ with respect to coupled cluster singles and doubles (CCSD) values. Removing SIE using PZ-SIC correctly reduces the DFA polarizabilities, but over-corrects, resulting in underestimated polarizabilities in SIC-LDA, -PBE, and -SCAN. Finally, we applied a recently proposed local-scaling 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 error of 0.08 Bohr$^3$ for LSIC-LDA and 0.06 Bohr$^3$ for LSIC-PBE with most recent CCSD polarizabilities. Likewise, the ionization energy estimates as an absolute of highest occupied energy eigenvalue predicted by LSIC are also in excellent agreement with CCSD(T) ionization energies with MAE of 0.4 eV for LSIC-LDA and 0.04 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 reported GW results.
Semi-local approximations to the density functional for the exchange-correlation energy of a many-electron system necessarily fail for lobed one-electron densities, including not only the familiar stretched densities but also the less familiar but cl
osely-related noded ones. The Perdew-Zunger (PZ) self-interaction correction (SIC) to a semi-local approximation makes that approximation exact for all one-electron ground- or excited-state densities and accurate for stretched bonds. When the minimization of the PZ total energy is made over real localized orbitals, the orbital densities can be noded, leading to energy errors in many-electron systems. Minimization over complex localized orbitals yields nodeless orbital densities, which reduce but typically do not eliminate the SIC errors of atomization energies. Other errors of PZ SIC remain, attributable to the loss of the exact constraints and appropriate norms that the semi-local approximations satisfy, and suggesting the need for a generalized SIC. These conclusions are supported by calculations for one-electron densities, and for many-electron molecules. While PZ SIC raises and improves the energy barriers of standard generalized gradient approximations (GGAs) and meta-GGAs, it reduces and often worsens the atomization energies of molecules. Thus PZ SIC raises the energy more as the nodality of the valence localized orbitals increases from atoms to molecules to transition states. PZ SIC is applied here in particular to the SCAN meta-GGA, for which the correlation part is already self-interaction-free. That property makes SCAN a natural first candidate for a generalized SIC.
(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 com
pared 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 corrections on 14 small to moderate-sized organic molecules relevant in organic electronics and polymer donor materials. Though 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 z{sigma}, 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.
Most widely used density functional approximations suffer from self-interaction (SI) error, which can be corrected using the Perdew-Zunger (PZ) self-interaction correction (SIC). We implement the recently proposed size-extensive formulation of PZ-SIC
using Fermi-Lowdin Orbitals (FLOs) in real space, which is amenable to systematic convergence and large-scale parallelization. We verify the new formulation within the generalized Slater scheme by computing atomization energies and ionization potentials of selected molecules and comparing to those obtained by existing FLOSIC implementations in Gaussian based codes. The results show good agreement between the two formulations, with new real-space results somewhat closer to experiment on average for the systems considered. We also obtain the ionization potentials and atomization energies by scaling down the Slater statistical average of SIC potentials. The results show that scaling down the average SIC potential improves both atomization energies and ionization potentials, bringing them closer to experiment. Finally, we verify the present formulation by calculating the barrier heights of chemical reactions in the BH6 dataset, where significant improvements are obtained relative to Gaussian based FLOSIC results.
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