Two-Dimensional Penning Ionization Electron Spectroscopy of Open-Shell Metallocenes: Outer Valence Ionic States of Vanadocene and Nickelocene

Kishimoto, Naoki; Kimura, M.; Ohno, Koichi

doi:10.1021/jp310308k

Cited by 3 publications

(2 citation statements)

References 33 publications

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“…4,21,22 Discoveries of novel chemical bonding in molecular anions were facilitated by convincing assignments of their photodetachment spectra. 23 Agreement between electron propagator calculations and experiment enabled deeper understanding of Penning ionization 24 spectra.…”

Section: ■ Introductionmentioning

confidence: 99%

“…With these efficient and flexible tools, valence photoelectron spectra of many molecules and molecular ions were assigned. ,, Discoveries of novel chemical bonding in molecular anions were facilitated by convincing assignments of their photodetachment spectra . Agreement between electron propagator calculations and experiment enabled deeper understanding of Penning ionization spectra.…”

Section: Introductionmentioning

confidence: 99%

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New-Generation Electron-Propagator Methods for Molecular Electron-Binding Energies

Opoku,

Pawłowski,

Ortiz

2024

J. Phys. Chem. A

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A new generation of electron-propagator methods for the calculation of electron binding energies has surpassed its antecedents with respect to accuracy, efficiency, and interpretability. No adjustable parameters are introduced in these fully ab initio procedures. Numerical tests versus several databases of valence, vertical electron binding energies of closed-shell molecules and atoms have been performed. Easily interpreted self-energy approximations with cubic arithmetic scaling produce mean absolute errors (MAEs) of 0.2 and 0.3 eV for electron detachments and attachments, respectively. The most accurate explicitly renormalized methods with fifth-power arithmetic scaling yield MAEs below 0.1 eV for detachments and attachments. Approximate renormalization leads to more efficient fifth-power alternatives for electron detachments that achieve similar accuracy with fewer bottleneck operations. Composite protocols generate excellent predictions versus highly accurate basis-extrapolated standards and experiments. The validity of the diagonal self-energy approximation and the accuracy of the approximate renormalizations are confirmed. The success of these perturbative methods based on canonical Hartree−Fock orbitals rests on a Hermitized, intermediately normalized superoperator metric. The results of all of the new-generation calculations may be analyzed in terms of final-state orbital relaxation and differential correlation effects.

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