English (United Kingdom)

https://curated-unify.zendy.io/wp-json/zendy-region/v1/featured_content/oa?rat=en

https://curated-unify.zendy.io/wp-json/zendy-region/v1/highlighted_journal/

Global: Zendy Plus annual

Presents the access of premium content as premium feature

Premium Content

Presents the keyphrase highlighting as premium feature

Keyphrase Highlighting

Presents the summarisation as premium feature

Summarisation

Insights

Presents the pdf analysis as premium feature

PDF Analysis

Presents the zaia usage as premium feature

ZAIA

Global: Zendy Tools annual

Global: Zendy Free Plan

Global: Zendy Tools monthly

Global: Zendy Plus monthly

Photoelectron spectra of early $3d-$transition metal dioxide anions,ScO$_{2}^-$, TiO$_{2}^-$, VO$_{2}^-$, CrO$_{2}^-$, MnO$_{2}^-$, are calculatedusing semilocal and hybrid density functional theory (DFT) and many-bodyperturbation theory within the $GW$ approximation using one-shot perturbativeand eigenvalue self-consistent formalisms. Different levels of theory arecompared with each other and with available photoelectron spectra. We show thatone-shot $GW$ with a PBE0 starting point ($G_0W_0$@PBE0) consistently providesvery good agreement for all experimentally measured binding energies (within0.1-0.2 eV or less), which we attribute to the success of PBE0 in mitigatingself-interaction error and providing good quasiparticle wave functions, whichrenders a first-order perturbative $GW$ correction effective. One-shot $GW$calculations with semilocal exchange in the DFT starting point (e.g.$G_0W_0$@PBE) do poorly in predicting electron removal energies by underbindingorbitals 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 goodagreement with experiment by overbinding orbitals with typical errors near 0.5eV. While not as accurate as $G_0W_0$@PBE0, the $G$-only eigenvalueself-consistent $GW$ scheme with $W$ fixed to the PBE level ($G_nW_0$@PBE)provides a reasonably predictive level of theory (typical errors near 0.3 eV)to describe photoelectron spectra of these $3d-$transition metal dioxideanions. Adding eigenvalue self-consistency also in $W$ ($G_nW_n$@PBE), on theother hand, worsens the agreement with experiment overall. Our findings on theperformance of various $GW$ methods are discussed in the context of ourprevious studies on other transition metal oxide molecular systems.

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