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

Abstract

Photoelectron spectra of early 3d-transition metal dioxide anions, ScO2−, TiO2−, VO2−, CrO2−, and MnO2−, 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 (G0W0@PBE0) consistently provides very good agreement for all experimentally measured binding energies (within 0.1 eV–0.2 eV or less). We attribute this 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 a Perdew–Burke–Ernzerhof (PBE) starting point do poorly in predicting electron removal energies by underbinding orbitals with typical errors near 1.5 eV. A higher exact exchange amount of 50% in the DFT starting point of one-shot GW does not provide very good agreement with experiment by overbinding orbitals with typical errors near 0.5 eV. While not as accurate as G0W0@PBE0, the G-only eigenvalue self-consistent GW scheme with W fixed to the PBE level 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, 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.

GW100: A Slater-Type Orbital Perspective

“…These results are the focus of the current work and are meant to complement the previous studies on GW100 using GTOs, PWs, and RSFEs. Since G 0 W 0 @PBE generally do not give accurate QP energies, ,, we will only focus on numerical aspects and abstain from comparison to experimental or high-level quantum chemistry reference values. , To complement our results, we also calculate IPs and EAs of 250 molecules from the GW5000 database . This work is organized as follows: in Section , we shortly outline the G 0 W 0 implementation in ADF and describe our new basis sets.…”

Low-Order Scaling Quasiparticle Self-Consistent GW for Molecules

“…The GW approximation (GWA) to Hedin's equations (Hedin, 1965) is a popular approach to calculate charged excitations in molecular systems. Recent applications include the calculation of band gaps and elucidation of charge-transfer in organic donor-acceptor compounds Caruso et al, 2014), applications to dye-sensitized solar cells (Marom et al, 2011;Faber et al, 2012;Umari et al, 2013;Marom et al, 2014;Mowbray and Migani, 2015), electronic level alignment in photocatalytic interfaces (Migani et al, 2013(Migani et al, , 2014, coreionization spectra of medium sized molecules (Van Setten et al, 2018;Golze et al, 2018Golze et al, , 2020 or photo-electron spectra of transition metal oxides (Berardo et al, 2017;Hung et al, 2017;Shi et al, 2018;Rezaei and Ögüt, 2021). Combined with the Bethe-Salpeter equation (BSE) formalism (Salpeter and Bethe, 1951;Strinati, 1988) the GWA has been used to calculate optical spectra of Cyanins (Boulanger et al, 2014), the Bacteriochlorin molecule (Duchemin et al, 2012) or Bacteriochlorophylls and Chlorophylls (Hashemi and Leppert, 2021).…”

Electron Propagator Theory of Vertical Electron Detachment Energies of Anions: Benchmarks and Applications to Nucleotides

“…Metal oxide cluster anions whose reactivity has implications for catalysis and related technologies have been studied with a view to assignment of photoelectron spectra. Aluminum oxide cluster anions, especially those with formal metal oxidation states below +3, may have spectra that correspond to more than one isomer. − Spectra of the products of reactions between these clusters and various molecules have been interpreted. , Silicon and transition-metal oxide clusters also have been considered. , …”

“…141,142 Silicon and transition-metal oxide clusters also have been considered. 143,144 Calculations of the electron detachment energies of double Rydberg anions have provided definitive assignments of photoelectron spectra and have offered testable predictions for further experimentation. Tetrahedral NH 4…”