Deutsch
 
Hilfe Datenschutzhinweis Impressum
  DetailsucheBrowse

Datensatz

DATENSATZ AKTIONENEXPORT
  A Restricted Open Configuration Interaction with Singles Method To Calculate Valence-to-Core Resonant X-ray Emission Spectra: A Case Study

Maganas, D., DeBeer, S., & Neese, F. (2017). A Restricted Open Configuration Interaction with Singles Method To Calculate Valence-to-Core Resonant X-ray Emission Spectra: A Case Study. Inorganic Chemistry, 56(19), 11819-11836. doi:10.1021/acs.inorgchem.7b01810.

Item is

Basisdaten

einblenden: ausblenden:
Genre: Zeitschriftenartikel

Externe Referenzen

einblenden:

Urheber

einblenden:
ausblenden:
 Urheber:
Maganas, Dimitrios1, Autor           
DeBeer, Serena1, Autor           
Neese, Frank1, Autor           
Affiliations:
1Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              

Inhalt

einblenden:
ausblenden:
Schlagwörter: -
 Zusammenfassung: In this work, a new protocol for the calculation of valence-to-core resonant X-ray emission (VtC RXES) spectra is introduced. The approach is based on the previously developed restricted open configuration interaction with singles (ROCIS) method and its parametrized version, based on a ground-state Kohn–Sham determinant (DFT/ROCIS) method. The ROCIS approach has the following features: (1) In the first step approximation, many-particle eigenstates are calculated in which the total spin is retained as a good quantum number. (2) The ground state with total spin S and excited states with spin S′ = S, S ± 1, are obtained. (3) These states have a qualitatively correct multiplet structure. (4) Quasi-degenerate perturbation theory is used to treat the spin–orbit coupling operator variationally at the many-particle level. (5) Transition moments are obtained between the relativistic many-particle states. The method has shown great potential in the field of X-ray spectroscopy, in particular in the field of transition-metal L-edge, which cannot be described correctly with particle–hole theories. In this work, the method is extended to the calculation of resonant VtC RXES [alternatively referred to as 1s-VtC resonant inelastic X-ray scattering (RIXS)] spectra. The complete Kramers–Dirac–Heisenerg equation is taken into account. Thus, state interference effects are treated naturally within this protocol. As a first application of this protocol, a computational study on the previously reported VtC RXES plane on a molecular managanese(V) complex is performed. Starting from conventional X-ray absorption spectra (XAS), we present a systematic study that involves calculations and electronic structure analysis of both the XAS and non-resonant and resonant VtC XES spectra. The very good agreement between theory and experiment, observed in all cases, allows us to unravel the complicated intensity mechanism of these spectroscopic techniques as a synergic function of state polarization and interference effects. In general, intense features in the RIXS spectra originate from absorption and emission processes that involve nonorthogonal transition moments. We also present a graphical method to determine the sign of the interference contributions.

Details

einblenden:
ausblenden:
Sprache(n): eng - English
 Datum: 2017-09-182017-10-02
 Publikationsstatus: Erschienen
 Seiten: 18
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/acs.inorgchem.7b01810
 Art des Abschluß: -

Veranstaltung

einblenden:

Entscheidung

einblenden:

Projektinformation

einblenden:

Quelle 1

einblenden:
ausblenden:
Titel: Inorganic Chemistry
  Kurztitel : Inorg. Chem.
Genre der Quelle: Zeitschrift
 Urheber:
Affiliations:
Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: - Band / Heft: 56 (19) Artikelnummer: - Start- / Endseite: 11819 - 11836 Identifikator: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669