Predicting core level binding energies shifts: Suitability of the projector augmented wave approach as implemented in VASP

Bellafont, Noèlia Pueyo; Viñes, Francesc; Hieringer, Wolfgang

doi:10.1002/jcc.24704

Cited by 54 publications

(66 citation statements)

References 34 publications

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“…The most common approaches are the ∆SCF method where the core-electron binding energy is calculated as the total energy difference between the ground state and the final state with a core hole, [15] and the related Slater-Janak transition state method [16,17]. These techniques yield relative core-electron binding energies, or binding energy shifts, that are in good agreement with experimental measurements for free molecules * j.lischner@imperial.ac.uk [18][19][20][21][22][23]. While calculated binding energy shifts are often very useful for the interpretation of XPS spectra, their use requires the existence of well-defined core-level reference energies which is not always guaranteed.…”

Section: Introductionmentioning

confidence: 90%

Accurate absolute core-electron binding energies of molecules, solids, and surfaces from first-principles calculations

Kahk

Lischner

2019

Phys. Rev. Materials

112

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Core-electron x-ray photoelectron spectroscopy is a powerful technique for studying the electronic structure and chemical composition of molecules, solids and surfaces. However, the interpretation of measured spectra and the assignment of peaks to atoms in specific chemical environments is often challenging. Here, we address this problem and introduce a parameter-free computational approach for calculating absolute core-electron binding energies. In particular, we demonstrate that accurate absolute binding energies can be obtained from the total energy difference of the ground state and a state with an explicit core hole when exchange and correlation effects are described by a recently developed meta-generalized gradient approximation and relativistic effects are included even for light elements. We carry out calculations for molecules, solids and surface species and find excellent agreement with available experimental measurements. For example, we find a mean absolute error of only 0.16 eV for a reference set of 103 molecular core-electron binding energies. The capability to calculate accurate absolute core-electron binding energies will enable new insights into a wide range of chemical surface processes that are studied by x-ray photoelectron spectroscopy. arXiv:1904.04823v1 [cond-mat.mtrl-sci]

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Section: Introductionmentioning

confidence: 90%

Accurate absolute core-electron binding energies of molecules, solids, and surfaces from first-principles calculations

Kahk

Lischner

2019

Phys. Rev. Materials

112

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“…Using the eigenvalues G m of G to compute the trace in Equation (38) and using Equations (4) and (37) yields Sum up: Figure 2: Pseudocode for the CD-G 0 W 0 method. Displayed is the computation of the QP energy G 0 W 0 n for state n.…”

Section: Spectral Functionmentioning

confidence: 99%

“…The CD-G 0 W 0 method contains the convergence parameter η, see Equations (33)(34)(35)(36)(37). The self-energy is broadened with increasing η, which eventually affects the QP solutions.…”

Section: Broadening Parameter ηmentioning

confidence: 99%

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Core-Level Binding Energies from GW: An Efficient Full-Frequency Approach within a Localized Basis

Golze

Wilhelm

Setten

et al. 2018

J. Chem. Theory Comput.

113

272

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The GW method is routinely used to predict charged valence excitations in molecules and solids. However, the numerical techniques employed in the most efficient GW algorithms break down when computing core excitations as measured by X-ray photoelectron spectroscopy (XPS). We present a full-frequency approach on the real axis using a localized basis to enable the treatment of core levels in GW. Our scheme is based on the contour deformation technique and allows for a precise and efficient calculation of the self-energy, which has a complicated pole structure for core states. The accuracy of our method is validated by comparing to a fully analytic GW algorithm. Furthermore, we report the obtained core-level binding energies and their deviations from experiment for a set of small molecules and large polycyclic hydrocarbons. The core-level excitations computed with our GW approach deviate by less than 0.5 eV from the experimental reference. For comparison, we also report core-level binding energies calculated by density functional theory (DFT)-based approaches such as the popular delta self-consistent field (ΔSCF) method. Our implementation is optimized for massively parallel execution, enabling the computation of systems up to 100 atoms.

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“…The cation ordering within the pristine materials and the Li + arrangement within the delithiated structures of the layered oxide were generated following the methodology described by Seo et al 4 and using the Python Materials Genomics tool (pymatgen). 44 The core level binding energies (E CL ) of the O 1s electrons were evaluated with the initial state approximation [45][46][47][48][49][50] and shied with respect to a reference system (Li 2 MnO 3 (ref. 51)) into the experimentally observed energy region.…”

Section: Ab Initio Simulationsmentioning

confidence: 99%

Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes

et al. 2019

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Lithium-rich materials, such as Li 1.2 Ni 0.2 Mn 0.6 O 2 , exhibit capacities not limited by transition metal redox, through the reversible oxidation of oxide anions. Here we offer detailed insight into the degree of oxygen redox as a function of depth within the material as it is charged and cycled. Energy-tuned photoelectron spectroscopy is used as a powerful, yet highly sensitive technique to probe electronic states of oxygen and transition metals from the top few nanometers at the near-surface through to the bulk of the particles. Two discrete oxygen species are identified, O nÀ and O 2À , where n < 2, confirming our previous model that oxidation generates localised hole states on O upon charging. This is in contrast to the oxygen redox inactive high voltage spinel LiNi 0.5 Mn 1.5 O 4 , for which no O nÀ species is detected. The depth profile results demonstrate a concentration gradient exists for O nÀ from the surface through to the bulk, indicating a preferential surface oxidation of the layered oxide particles. This is highly consistent with the already well-established core-shell model for such materials. Ab initio calculations reaffirm the electronic structure differences observed experimentally between the surface and bulk, while modelling of delithiated structures shows good agreement between experimental and calculated binding energies for O nÀ .

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Predicting core level binding energies shifts: Suitability of the projector augmented wave approach as implemented in VASP

Cited by 54 publications

References 34 publications

Accurate absolute core-electron binding energies of molecules, solids, and surfaces from first-principles calculations

Accurate absolute core-electron binding energies of molecules, solids, and surfaces from first-principles calculations

Core-Level Binding Energies from GW: An Efficient Full-Frequency Approach within a Localized Basis

Depth-dependent oxygen redox activity in lithium-rich layered oxide cathodes

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