Improved charge transfer multiplet method to simulate M- and L-edge X-ray absorption spectra of metal-centered excited states.

@article{Zhang2018ImprovedCT,
  title={Improved charge transfer multiplet method to simulate M- and L-edge X-ray absorption spectra of metal-centered excited states.},
  author={Kaili Zhang and Gregory S. Girolami and Josh Vura-Weis},
  journal={Journal of synchrotron radiation},
  year={2018},
  volume={25 Pt 5},
  pages={
          1600-1608
        }
}
Charge transfer multiplet (CTM) theory is a computationally undemanding and highly mature method for simulating the soft X-ray spectra of first-row transition metal complexes. However, CTM theory has seldom been applied to the simulation of excited-state spectra. In this article, the CTM4XAS software package is extended to simulate M2,3- and L2,3-edge spectra for the excited states of first-row transition metals and also interpret CTM eigenfunctions in terms of Russell-Saunders term symbols… 
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References

SHOWING 1-10 OF 61 REFERENCES
Tabletop Femtosecond M-edge X-ray Absorption Near-Edge Structure of FeTPPCl: Metalloporphyrin Photophysics from the Perspective of the Metal.
TLDR
This work directly probes the metal center of iron(III) tetraphenyl porphyrin chloride using femtosecond M2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy, and introduces tabletop M- edge XANES as a valuable tool for measuring femTosecond dynamics of molecular transition metal complexes in the condensed phase.
Characterization of Photo-Induced Charge Transfer and Hot Carrier Relaxation Pathways in Spinel Cobalt Oxide (Co3O4)
The identities of photoexcited states in thin-film Co3O4 and the ultrafast carrier relaxation dynamics of Co3O4 are investigated with oxidation-state-specific pump–probe femtosecond core level…
Ab Initio Calculations of X-ray Spectra: Atomic Multiplet and Molecular Orbital Effects in a Multiconfigurational SCF Approach to the L-Edge Spectra of Transition Metal Complexes.
TLDR
The authors' quantum chemical calculations on a high level of accuracy in a post-Hartree-Fock framework give excellent agreement with experiment and opens the door to reliable and detailed information on chemical interactions and the valence electronic structure in 3d transition-metal complexes also in transient excited electronic states.
Ligand-field symmetry effects in Fe(II) polypyridyl compounds probed by transient X-ray absorption spectroscopy.
TLDR
It is demonstrated that ground-state and, more importantly, ultrafast time-resolved X-ray absorption methods can offer unique insights into the interplay between electronic and geometric structure that underpins the photo-induced dynamics of this class of compounds.
Strong double excitation and open-shell features in the near-edge x-ray absorption fine structure spectroscopy of ferrocene and ferrocenium compounds.
TLDR
The CI calculations indicate that double excitation is essential to interpret the Fe 2p NEXAFS spectra of not only the open- shell ferrocenium ion but also the closed-shell ferrocene species, even though the ground states of both species are well described within the Hartree-Fock single-configuration approximation.
Femtosecond M2,3-Edge Spectroscopy of Transition-Metal Oxides: Photoinduced Oxidation State Change in α-Fe2O3
Oxidation-state-specific dynamics at the Fe M2,3-edge are measured on the sub-100 fs time scale using tabletop high-harmonic extreme ultraviolet spectroscopy. Transient absorption spectroscopy of…
Element-specific characterization of transient electronic structure of solvated Fe(II) complexes with time-resolved soft X-ray absorption spectroscopy.
TLDR
Progress is presented in employing picosecond and femtosecond soft X-ray pulses from synchrotron sources to investigate element specific valence charge distributions and spin-state evolutions in Fe(II) polypyridyl complexes via core-level transitions.
Hitchhiker's guide to multiplet calculations
Core level spectra from localized magnetic systems, such as 3d transition metal compounds or rare earths, obtained with high resolution synchrotron radiation can be simulated theoretically by…
Iron L-Edge Absorption Spectroscopy of Iron Pentacarbonyl and Ferrocene in the Gas Phase.
TLDR
Experimental benchmark spectra for new ab initio approaches for calculating metal L-edge absorption spectra of metal complexes are provided and demonstrate how the interplay of local atomic multiplet effects and orbital interactions in the metal-ligand bonds varies for the different systems.
The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges.
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