Erratum: Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces [Phys. Rev. Lett.<b>100</b>, 136406 (2008)]

Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.; Vydrov, Oleg A.; Scuseria, Gustavo E.; Constantin, Lucian A.; Zhou, Xiaobo; Burke, Kieron

doi:10.1103/physrevlett.102.039902

Cited by 1,350 publications

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“…These opposite deviations from the experimental measurement have been attributed to the "overbinding" character of LDA and the consequent overcorrection of this defect in GGA [41,42]. However, we are more interested in comparing the relative stabilities of different surfaces than in assessing the different performances of LDA and GGA functionals, especially in the absence of the experimental data.…”

Section: Resultsmentioning

confidence: 99%

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

Sun

Liu

Song

et al. 2012

Journal of Nuclear Materials

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The (111), (110), and (001) surfaces properties of PuO 2 are studied by using density-functional theory+U method. The total-energy static calculations determine the relative order of stability for low-index PuO 2 surfaces, namely, O-terminated (111) > (110) > defective (001) > polar (001).The effect of thickness is shown to modestly modulate the surface stability and chemical activity of the (110) (111) is found to be the most stable surface. Whereas under O-reducing conditions, the on-surface O-vacancy of C V = 1/9 is stable, and for high reducing conditions, the (111) surface with nearly one monolayer subsurface oxygen removed (C V = 8/9) becomes most stable.

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Section: Resultsmentioning

confidence: 99%

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

Sun

Liu

Song

et al. 2012

Journal of Nuclear Materials

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“…51,52 The generalized gradient approximation (GGA) was employed using the Perdew-Burke-Ernzerhof (PBE) exchange and correlation functional for total energy and electronic structure cal-culations, 53 and the PBEsol functional for calculations of phonon dispersions and dielectric properties. 54 In each case, calculations were performed from structures with lattice parameters relaxed with the corresponding functional. Valence electron configurations were as follows: Cs, 5s 2 5p 6 6s 1 ; Br, 4s 2 4p 5 ; Sn, 5s 2 4d 10 5p 2 ; Pb, 6s 2 5d 10 6p 2 ; Ca, 3s 2 3p 6 4s 2 .…”

Section: Methodsmentioning

confidence: 99%

Dynamic Stereochemical Activity of the Sn²⁺ Lone Pair in Perovskite CsSnBr₃

et al. 2016

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Stable s 2 lone pair electrons on heavy main-group elements in their lower oxidation states drive a range of important phenomena, such as the emergence of polar ground states in some ferroic materials. Here we study the perovskite halide CsSnBr 3 as an embodiment of the broader materials class. We show that lone pair stereochemical activity due to the Sn s 2 lone pair causes a crystallographically hidden, locally distorted state to appear upon warming, a phenomenon previously referred to as emphanisis.The synchrotron X-ray pair distribution function acquired between 300 K and 420 K reveals emerging asymmetry in the nearest-neighbor Sn-Br correlations, consistent with dynamic Sn 2+ off-centering, despite there being no evidence of any deviation from the average cubic structure. Computation based on density functional theory supports the finding of a lattice instability associated with dynamic off-centering of Sn 2+ in its coordination environment. Photoluminescence measurements reveal an unusual blueshift with increasing temperature, closely linked to the structural evolution. At low temperatures, the structures reflect the influence of octahedral rotation. A continuous transition from an orthorhombic structure (P nma, no. 62) to a tetragonal structure (P 4/mbm, no. 127) is found around 250 K, with a final, first-order transformation at 286 K to the cubic structure (P m3m, no. 221).2

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“…42 Concerning the exchangecorrelation functionals, we have used the following ones: Perdew− Zunger parametrization of the Ceperley−Alder free-electron gas correlation results in the local density approximation 43 (LDA); a PBEsol functional designed specifically to improve the generalized gradient approximation (GGA) in solids. 44 Apart from these, we have also employed hybrid functionals (with respectively 16% and 20% of Hartree−Fock exchange) such as the B1WC 45 and PW1PW. 46 These hybrid functionals allow one to obtain geometries, band gaps, and thermochemistry properties with great accuracy and reliability without the need for semiempirical parameters like in DFT+U procedures.…”

Section: Computational Detailsmentioning

confidence: 99%

Origin of Small Barriers in Jahn–Teller Systems: Quantifying the Role of 3d–4s Hybridization in the Model System NaCl:Ni⁺

Barriuso¹,

Ortiz-Sevilla²,

Aramburu³

et al. 2013

Inorg. Chem.

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Despite its relevance, the microscopic origin of the energy barrier, B, between the compressed and elongated geometries of Jahn−Teller (JT) systems is not well understood yet because of a lack of quantitative data about its various contributions. Seeking to clear up this matter, we have carried out both periodic and cluster ab initio calculations on the model system NaCl:Ni + . This system is particularly puzzling because, according to experimental data, its barrier is much smaller than that for other d 9 and d 7 ions in similar lattices. All calculations performed on the model system lead, in fact, to values |B| ≤ 160 cm −1 , which are certainly smaller than B = 500 cm −1 derived for NaCl:M 2+ (M = Ag, Rh) or B = 1024 cm −1 obtained for KCl:Ag 2+ . As a salient feature, analysis of calculations carried out as a function of the Q θ (∼3z 2 − r 2 ) coordinate unveils the microscopic origin of the barrier. It is quantitatively proven that the elongated geometry observed for NaCl:Ni + is due to the 3d−4s vibronic admixture, which is slightly larger than the anharmonicity in the e g JT mode that favors a compressed geometry. The existence of these two competing mechanisms explains the low value of B for the model system, contrary to cases where the complex formed by d 9 or d 7 ions is elastically decoupled from the host lattice. Although the magnitude of B for NaCl:Ni + is particularly small, the tunneling splitting, 3Γ, is estimated to be below 9 cm −1 , thus explaining why the coherence is easily destroyed by random strains and thus a static JT effect is observed experimentally. As a main conclusion, the barrier in JT systems cannot be understood neglecting the tiny changes of the electronic density involved in small distortions. The present calculations reasonably explain the experimental g tensor of NaCl:Ni + , pointing out that the d−d transitions in NiCl 6 5− are much smaller than those for CuCl 6 4− and the optical electronegativity of Ni + is only around 1.

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Erratum: Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces [Phys. Rev. Lett.100, 136406 (2008)]

Cited by 1,350 publications

References 0 publications

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

Dynamic Stereochemical Activity of the Sn²⁺ Lone Pair in Perovskite CsSnBr₃

Origin of Small Barriers in Jahn–Teller Systems: Quantifying the Role of 3d–4s Hybridization in the Model System NaCl:Ni⁺

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Erratum: Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces [Phys. Rev. Lett.100, 136406 (2008)]

Cited by 1,350 publications

References 0 publications

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

First-principles study of surface properties of PuO2: Effects of thickness and O-vacancy on surface stability and chemical activity

Dynamic Stereochemical Activity of the Sn2+ Lone Pair in Perovskite CsSnBr3

Origin of Small Barriers in Jahn–Teller Systems: Quantifying the Role of 3d–4s Hybridization in the Model System NaCl:Ni+

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Dynamic Stereochemical Activity of the Sn²⁺ Lone Pair in Perovskite CsSnBr₃

Origin of Small Barriers in Jahn–Teller Systems: Quantifying the Role of 3d–4s Hybridization in the Model System NaCl:Ni⁺