Recent advances in X-ray instrumentation have made it possible to measure the spectra of an essentially unexplored class of electronic states associated with double inner-shell vacancies. Using the technique of single electron spectroscopy, spectra of states in CS and SF with a double hole in the K-shell and one electron exited to a normally unoccupied orbital have been obtained. The spectra are interpreted with the aid of a high-level theoretical model giving excellent agreement with the experiment. The results shed new light on the important distinction between direct and conjugate shake-up in a molecular context. In particular, systematic similarities and differences between pre-edge states near single core holes investigated in X-ray absorption spectra and the corresponding states near double core holes studied here are brought out.
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http://dx.doi.org/10.1038/s41598-017-13607-6 | DOI Listing |
Inorg Chem
January 2025
Radiation Science & Technology Department, Faculty of Applied Sciences, Delft University of Technology, Mekelweg 15, Delft 2629JB, The Netherlands.
The detailed crystal structure as well as the heat capacity at low temperature and standard entropy of BaMoO are reported for the first time. High-resolution X-ray and neutron diffraction were employed to reveal the structural features of this compound. BaMoO has a six-coordinated Mo and a strongly negative excess volume with respect to the binary oxides.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemical Engineering, Virginia Tech, Blacksburg, Virginia 24061, United States.
The decomposition of ozone on supported manganese oxide catalysts, studied here, exemplifies reactions involving electron transfer. In situ extended X-ray absorption fine-structure spectra (Mn K-edge) on in situ treated samples show that the supported phase in MnO/SiO resembles MnO while that in MnO/AlO samples resembles MnO. In situ Raman spectroscopy shows the involvement of a common peroxide surface species.
View Article and Find Full Text PDFJ Phys Chem Lett
December 2024
Stanford PULSE Institute, SLAC National Accelerator Laboratory, Stanford University, Menlo Park, California 94025, United States.
Ni 2,2'-bipyridine complexes are commonly invoked intermediates in metallaphotoredox cross-coupling reactions. Despite their ubiquity, design principles targeting improved catalytic performance remain underdetermined. A series of Ni(bpy)(Ar)Cl (R = MeOOC, -Bu, R' = CH, CF) complexes were proposed to have multiconfigurational electronic structures on the basis of multiconfigurational/multireference calculations, with significant mixing of Ni → bpy metal-to-ligand charge transfer (MLCT) configurations into the ground-state wave function.
View Article and Find Full Text PDFJ Phys Chem A
December 2024
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilheim-Platz 1, 45470 Mülheim an der Ruhr, Germany.
In this work, we present a generalized implementation of the previously developed restricted open-shell configuration interaction singles (ROCIS) family of methods. The new method allows us to treat high-spin (HS) ferro- as well as antiferromagnetically (AF) coupled systems while retaining the total spin as a good quantum number. To achieve this important and nontrivial goal, we employ the machinery of the iterative configuration expansion (ICE) method, which is able to tackle general configuration interaction (CI) problems on the basis of spin-adapted configuration state functions (CSFs).
View Article and Find Full Text PDFChem Mater
November 2024
Department of Materials, Oxford University, Oxford OX1 3PH, U.K.
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