Correction to Benchmarking the <i>GW</i> Approximation and Bethe–Salpeter Equation for Groups IB and IIB Monoxides

Hung, Linda; Bruneval, Fabien; Baishya, Kopinjol; Öğüt, Serdar

doi:10.1021/acs.jctc.7b01054

Cited by 4 publications

(1 citation statement)

References 12 publications

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“…Accordingly, there have been much fewer studies on the performance of the GW approximation for systems that contain transition metal elements. Motivated by this observation, here we continue with our recent benchmark studies 37,38,42,43 by focusing on the electronic structure of nega) Electronic mail: ogut@uic.edu. atively charged 3d-transition metal dioxide clusters TMO − 2 , for TM = Sc, Ti, V, Cr, and Mn.…”

Section: Introductionmentioning

confidence: 99%

Photoelectron spectra of early $3d$-transition metal dioxide cluster anions from $GW$ calculations

Rezaei,

Öğüt

2020

Preprint

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Photoelectron spectra of early 3d−transition metal dioxide anions, ScO − 2 , TiO − 2 , VO − 2 , CrO − 2 , MnO − 2 , are calculated using semilocal and hybrid density functional theory (DFT) and many-body perturbation theory within the GW approximation using one-shot perturbative and eigenvalue self-consistent formalisms. Different levels of theory are compared with each other and with available photoelectron spectra. We show that one-shot GW with a PBE0 starting point (G 0 W 0 @PBE0) consistently provides very good agreement for all experimentally measured binding energies (within 0.1-0.2 eV or less), which we attribute to the success of PBE0 in mitigating self-interaction error and providing good quasiparticle wave functions, which renders a first-order perturbative GW correction effective. One-shot GW calculations with semilocal exchange in the DFT starting point (e.g. G 0 W 0 @PBE) do poorly in predicting electron removal energies by underbinding orbitals with typical errors near 1.5 eV. Higher amounts of exact exchange (e.g. 50%) in the DFT starting point of one-shot GW do not provide very good agreement with experiment by overbinding orbitals with typical errors near 0.5 eV. While not as accurate as G 0 W 0 @PBE0, the G-only eigenvalue self-consistent GW scheme with W fixed to the PBE level (G n W 0 @PBE) provides a reasonably predictive level of theory (typical errors near 0.3 eV) to describe photoelectron spectra of these 3d−transition metal dioxide anions. Adding eigenvalue self-consistency also in W (G n W n @PBE), on the other hand, worsens the agreement with experiment overall. Our findings on the performance of various GW methods are discussed in the context of our previous studies on other transition metal oxide molecular systems.

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Section: Introductionmentioning

confidence: 99%

Photoelectron spectra of early $3d$-transition metal dioxide cluster anions from $GW$ calculations

Rezaei,

Öğüt

2020

Preprint

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Photoelectron spectra of copper oxide cluster anions from first principles methods

Shi

Weissman

Bruneval

et al. 2018

The Journal of Chemical Physics

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We present results and analyses for the photoelectron spectra of small copper oxide cluster anions (CuO, Cu , Cu , and CuO). The spectra are computed using various techniques, including density functional theory (DFT) with semi-local, global hybrid, and optimally tuned range-separated hybrid functionals, as well as many-body perturbation theory within the approximation based on various DFT starting points. The results are compared with each other and with the available experimental data. We conclude that as in many metal-organic systems, self-interaction errors are a major issue that is mitigated by hybrid functionals. However, these need to be balanced against a strong role of non-dynamical correlation-especially in smaller, more symmetric systems-where errors are alleviated by semi-local functionals. The relative importance of the two phenomena, including practical ways of balancing the two constraints, is discussed in detail.

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Practical GW scheme for electronic structure of 3d-transition-metal monoxide anions: ScO−, TiO−, CuO−, and ZnO−

Byun

Öğüt

2019

The Journal of Chemical Physics

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The GW approximation to many-body perturbation theory is a reliable tool for describing charged electronic excitations, and it has been successfully applied to a wide range of extended systems for several decades using a plane-wave basis. However, the GW approximation has been used to test limited spectral properties of a limited set of finite systems (e.g., frontier orbital energies of closed-shell sp molecules) only for about a decade using a local-orbital basis. Here, we calculate the quasiparticle spectra of closed- and open-shell molecular anions with partially and completely filled 3d shells (shallow and deep 3d states, respectively), ScO−, TiO−, CuO−, and ZnO−, using various levels of GW theory, and compare them to experiments to evaluate the performance of the GW approximation on the electronic structure of small molecules containing 3d transition metals. We find that the G-only eigenvalue self-consistent GW scheme with W fixed to the PBE level (GnW0@PBE), which gives the best compromise between accuracy and efficiency for solids, also gives good results for both localized (d) and delocalized (sp) states of 3d-transition-metal oxide molecules. The success of GnW0@PBE in predicting electronic excitations in these systems reasonably well is likely due to the fortuitous cancellation effect between the overscreening of the Coulomb interaction by PBE and the underscreening by the neglect of vertex corrections. Together with the absence of the self-consistent field convergence error (e.g., spin contamination in open-shell systems) and the GW multisolution issue, the GnW0@PBE scheme gives the possibility to predict the electronic structure of complex real systems (e.g., molecule-solid and sp-d hybrid systems) accurately and efficiently.

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Correction to Benchmarking the GW Approximation and Bethe–Salpeter Equation for Groups IB and IIB Monoxides

Cited by 4 publications

References 12 publications

Photoelectron spectra of early $3d$-transition metal dioxide cluster anions from $GW$ calculations

Photoelectron spectra of early $3d$-transition metal dioxide cluster anions from $GW$ calculations

Photoelectron spectra of copper oxide cluster anions from first principles methods

Practical GW scheme for electronic structure of 3d-transition-metal monoxide anions: ScO−, TiO−, CuO−, and ZnO−

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