Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction

Withanage, Kushantha; Akter, Sharmin; Shahi, Chandra; Joshi, Ritesh; Diaz, Carlos M.; Yamamoto, Yoh; Zope, Rajendra R.; Baruah, Tunna; Perdew, John P.; Peralta, Juan E.; Jackson, Koblar Alan

doi:10.1103/physreva.100.012505

Cited by 37 publications

(31 citation statements)

References 39 publications

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“…The FLOSIC method has been implemented in Gaussian-orbital-based packages and has been successfully applied to study a wide array of electronic properties. 15,16,44,[57][58][59][60][62][63][64][65][66][67][76][77][78][79] In this work, we present a formulation and implementation of the FLOSIC method in real space. The real-space formulation enables rigorous, systematic convergence for all atomic species and configurations as well as large-scale parallelism to reach larger length and time scales than previously accessible at this level of theory.…”

Section: B Fermi-löwdin Orbitals Sic (Flosic)mentioning

confidence: 99%

Implementation of Perdew–Zunger self-interaction correction in real space using Fermi–Löwdin orbitals

Diaz

Suryanarayana

et al. 2021

The Journal of Chemical Physics

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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-Löwdin 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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Section: B Fermi-löwdin Orbitals Sic (Flosic)mentioning

confidence: 99%

Implementation of Perdew–Zunger self-interaction correction in real space using Fermi–Löwdin orbitals

Diaz

Suryanarayana

et al. 2021

The Journal of Chemical Physics

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“…It should be noted that other approaches have also been proposed in the literature to correct the SIE in DFT calculations. 121,122 3 Computational details…”

Section: Density-corrected Dftmentioning

confidence: 99%

General Many-Body Framework for Data-Driven Potentials with Arbitrary Quantum Mechanical Accuracy: Water as a Case Study

Lambros¹,

Dasgupta²,

Palos³

et al. 2021

Preprint

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<div> <div> <div> <p> </p><div> <div> <div> <p>We present a general framework for the development of data-driven many-body (MB) potential energy functions (MB-QM PEFs) that represent the interactions between small molecules at an arbitrary quantum-mechanical (QM) level of theory. As a demonstration, a family of MB-QM PEFs for water are rigorously derived from density functionals belonging to differ- ent rungs across Jacob’s ladder of approximations within density functional theory (MB-DFT) as well as from Møller-Plesset perturbation theory (MB-MP2). Through a systematic analysis of individual many-body contributions to the interaction energies of water clusters, we demonstrate that all MB-QM PEFs preserve the same accuracy as the corresponding ab initio calculations, with the exception of those derived from density functionals within the generalized gradient approximation (GGA). The differences between the DFT and MB-DFT results are traced back to density-driven errors that prevent GGA functionals from accurately representing the underlying molecular interactions for different cluster sizes and hydrogen-bonding arrangements. We show that this shortcoming may be overcome, within the many-body formalism, by using density-corrected functionals that provide a more consistent representation of each individual many-body contribution. This is demonstrated through the development of a MB-DFT PEF derived from density-corrected PBE-D3 data, which more accurately reproduce the corresponding ab initio results. </p> </div> </div> </div> </div> </div> </div>

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“…This model relies on accurate static polarizabilities from higher-level calculations 43,44 and predicts the vdW interaction from the C 3 and C 5 coefficients and the distances between the particle and surface plane through an expression whose large -z asymptote is…”

Section: Benchmark Binding Energies For the Adsorption Of Thiophene Omentioning

confidence: 99%

Molecule-surface interaction from van der Waals-corrected semilocal density functionals: The example of thiophene on transition-metal surfaces

Adhikari

Tang

Neupane

et al. 2020

Phys. Rev. Materials

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Semi-local density functional approximations are widely used. None of them can capture the long-range van der Waals (vdW) attraction between separated subsystems, but they differ remarkably in the extent to which they capture intermediate-range vdW effects responsible for equilibrium bonds between neighboring small closed-shell subsystems. The local density approximation (LDA) often overestimates this effect, while the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) underestimates it. The strongly-constrained and appropriately normed (SCAN) meta-GGA often estimates it well. All of these semi-local functionals require an additive non-local 1 arXiv:1906.01091v2 [cond-mat.mtrl-sci] 5 Jun 2019 correction such as the revised Vydrov-Van Voorhis 2010 (rVV10) to capture the longrange part. This work reports adsorption energies and the corresponding geometry of the aromatic thiophene (C 4 H 4 S) bound to transition metal surfaces. The adsorption process requires a genuine interplay of covalent and weak binding and requires a simultaneously accurate description of surface and adsorption energies with the correct prediction of the adsorption site. All these quantities must come from well balanced short and long-range correlation effects for a universally applicable method for weak interactions with chemical accuracy.

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Self-interaction-free electric dipole polarizabilities for atoms and their ions using the Fermi-Löwdin self-interaction correction

Cited by 37 publications

References 39 publications

Implementation of Perdew–Zunger self-interaction correction in real space using Fermi–Löwdin orbitals

Implementation of Perdew–Zunger self-interaction correction in real space using Fermi–Löwdin orbitals

General Many-Body Framework for Data-Driven Potentials with Arbitrary Quantum Mechanical Accuracy: Water as a Case Study

Molecule-surface interaction from van der Waals-corrected semilocal density functionals: The example of thiophene on transition-metal surfaces

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