The Influence of One-Electron Self-Interaction on d-Electrons

Schmidt, Tobias; Kümmel, Stephan

doi:10.3390/computation4030033

Cited by 13 publications

(16 citation statements)

References 125 publications

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“…Schmidt et al [18] discuss the influence of one-electron self-interaction on d-electrons and analyze two variants of hybrid functionals. They are applied to study four diatomic molecules containing transition metals.…”

Section: Contentmentioning

confidence: 99%

Special Issue “50th Anniversary of the Kohn–Sham Theory—Advances in Density Functional Theory”

Nagy

Schwarz

2016

Computation

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Section: Contentmentioning

confidence: 99%

Special Issue “50th Anniversary of the Kohn–Sham Theory—Advances in Density Functional Theory”

Nagy

Schwarz

2016

Computation

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“…10 Systems with d or f electrons containing both localized orbitals and delocalized orbitals are genuinely plagued by the SIE. 11 A natural solution to these challenges, the adiabatic connection fluctuationdissipation (ACFD) formulation of density functional theory (DFT) is constructed from a self-interaction free exchange energy and a non-local correlation energy that directly accounts for dispersion. [12][13][14] The Random Phase Approximation (RPA) is the simplest approximation within ACFD-DFT and has proven to be a highly accurate method for treating weak interactions [15][16][17][18][19] and predicting structural properties [20][21][22][23][24] and energetics 25,26 .…”

Section: Introductionmentioning

confidence: 99%

From semilocal density functionals to random phase approximation renormalized perturbation theory: A methodological assessment of structural phase transitions

2018

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The structural phase transitions of different materials, including metal to metal, metal to semiconductor and semiconductor to semiconductor transitions, were explored using methods based on the Random Phase Approximation. Transition pressures for Si, Ge, SiC, GaAs, SiO2, Pb, C, and BN from their stable low-pressure phases to certain high-pressure phases were computed with several semilocal density functionals and from the adiabatic connection fluctuation-dissipation formulation of density functional theory at zero temperature. In addition to the Random Phase Approximation (RPA), three approximate beyond-RPA methods were also investigated to determine the impact of exchange-correlation kernel corrections. Results at finite temperature were obtained with the inclusion of zero-point energy contributions from the phonon spectra. We find that including termperature effects is most important for systems with nearly degenerate phases such as for boron nitride and carbon. In combination with thermal corrections, the kernel-corrected correlation methods deliver high accuracy compared to experimental data and can serve as a useful benchmark method in place of more expensive correlated calculations.

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“…It was repeatedly argued that functionals affected by electronic self-interaction erroneously shift states from localized orbitals to higher energies, while delocalized states suffer less from self-interaction 53,54,[65][66][67][68][69][70][71][72][73] . In the context of Pd@SiCN, in particular the cancellation of self-interaction for localized orbitals originating from d-states is important 6,50,74,75 .…”

Section: Analyzing the Density Of Statesmentioning

confidence: 99%

“…Primarily we use the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) 47,48 . However, we address the question of electronic self-interaction 49 , which may affect the energetic position of states emerging from localized d-states 50 , by also evaluating the DOS with the PBE0 51 and BHLYP 52 hybrid functionals. These partially counteract self-interaction 50,53,54 .…”

Section: Motivationmentioning

confidence: 99%

“…However, we address the question of electronic self-interaction 49 , which may affect the energetic position of states emerging from localized d-states 50 , by also evaluating the DOS with the PBE0 51 and BHLYP 52 hybrid functionals. These partially counteract self-interaction 50,53,54 . We thus ensure that the influence of the support on the electronic structure of the nanoparticle is not merely a feature observed for a particular density functional, but is truly of systematic character.…”

Section: Motivationmentioning

confidence: 99%

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Investigating the electronic structure of a supported metal nanoparticle: Pd in SiCN

Schmidt

Albuquerque

Kempe

et al. 2016

Phys. Chem. Chem. Phys.

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We investigate the electronic structure of a Palladium nanoparticle that is partially embedded in a matrix of silicon carbonitride. From classical molecular dynamics simulations we first obtain a representative atomic structure. This geometry then serves as input to density-functional theory calculations that allow us to access the electronic structure of the combined system of particle and matrix. In order to make the computations feasible, we devise a subsystem strategy for calculating the relevant electronic properties. We analyze the Kohn-Sham density of states and pay particular attention to d-states which are prone to be affected by electronic self-interaction. We find that the density of states close to the Fermi level is dominated by states that originate from the Palladium nanoparticle. The matrix has little direct effect on the electronic structure of the metal. Our results contribute to explaining why silicon carbonitride does not have detrimental effects on the catalytic properties of palladium particles and can serve positively as a stabilizing mechanical support. MotivationFirst-principles electronic-structure theory 1-13 allows to gain unbiased insights into the microscopic, quantum-mechanical effects that are at the heart of modern nanotechnology [14][15][16][17][18][19][20][21][22][23][24] . However, often full ab-initio studies on systems of experimental relevance remain challenging since the computational effort grows immensely with system size 25 . For instance, in many experiments metal nanoparticles that have a diameter of several nm and contain several hundreds or thousands of atoms are used. For such systems, tens of thousands of electrons have to be taken into account for first-principles studies. Even with modern computers using massive parallelization, geometry optimizations and detailed investigations of the electronic structure of systems of that size are out of reach. Therefore, strategies have to be devised how insights can be gained into large systems despite of these computational limitations. In this work, we take a first step in this direction and investigate a palladium nanoparticle which is partially embedded in a matrix of silicon carbonitride (SiCN).This system is of practical relevance because noble-metal nanoparticles, in particular nanoparticles containing Pd, are effective catalysts for a wide range of chemical reactions [26][27][28][29][30] . In comparison to bulk metals, nanoparticles exhibit a high surface-

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The Influence of One-Electron Self-Interaction on d-Electrons

Cited by 13 publications

References 125 publications

Special Issue “50th Anniversary of the Kohn–Sham Theory—Advances in Density Functional Theory”

Special Issue “50th Anniversary of the Kohn–Sham Theory—Advances in Density Functional Theory”

From semilocal density functionals to random phase approximation renormalized perturbation theory: A methodological assessment of structural phase transitions

Investigating the electronic structure of a supported metal nanoparticle: Pd in SiCN

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