Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy
Abstract
Metal centers in transition metal–ligand complexes occur in a variety of oxidation states causing their redox activity and therefore making them relevant for applications in physics and chemistry. The electronic state of these complexes can be studied by X-ray absorption spectroscopy, which is, however, due to the complex spectral signature not always straightforward. Here, we study the electronic structure of gas-phase cationic manganese acetylacetonate complexes Mn(acac)1–3+ using X-ray absorption spectroscopy at the metal center and ligand constituents. The spectra are well reproduced by multiconfigurational wave function theory, time-dependent density functional theory as well as parameterized crystal field and charge transfer multiplet simulations. This enables us to get detailed insights into the electronic structure of ground-state Mn(acac)1–3+ and extract empirical parameters such as crystal field strength and exchange coupling from X-ray excitation at both the metal and ligand sites. By comparison to X-ray absorption spectra of neutral, solvated Mn(acac)2,3 complexes, we also show that the effect of coordination on the L3 excitation energy, routinely used to identify oxidation states, can contribute about 40–50% to the observed shift, which for the current study is 1.9 eV per oxidation state.
- Authors:
-
[2];
[3];
[3];
[4];
[1];
[3]
- Univ. of Freiburg (Germany); Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Uppsala Univ. (Sweden)
- Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy
- Uppsala Univ. (Sweden)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); German Federal Ministry of Education and Research (BMBF); Swedish Research Council (SRC)
- OSTI Identifier:
- 1998754
- Grant/Contract Number:
- AC02-76SF00515; BMBF-05K16VF1; VR 2022-04794; 2018-05973
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 127; Journal Issue: 34; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical calculations; electronic structure; energy; oxidation state; transition metals
Citation Formats
Ablyasova, Olesya S., Guo, Meiyuan, Zamudio-Bayer, Vicente, Kubin, Markus, Gitzinger, Tim, da Silva Santos, Mayara, Flach, Max, Timm, Martin, Lundberg, Marcus, Lau, J. Tobias, and Hirsch, Konstantin. Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy. United States: N. p., 2023.
Web. doi:10.1021/acs.jpca.3c02794.
Ablyasova, Olesya S., Guo, Meiyuan, Zamudio-Bayer, Vicente, Kubin, Markus, Gitzinger, Tim, da Silva Santos, Mayara, Flach, Max, Timm, Martin, Lundberg, Marcus, Lau, J. Tobias, & Hirsch, Konstantin. Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy. United States. https://doi.org/10.1021/acs.jpca.3c02794
Ablyasova, Olesya S., Guo, Meiyuan, Zamudio-Bayer, Vicente, Kubin, Markus, Gitzinger, Tim, da Silva Santos, Mayara, Flach, Max, Timm, Martin, Lundberg, Marcus, Lau, J. Tobias, and Hirsch, Konstantin. Thu .
"Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy". United States. https://doi.org/10.1021/acs.jpca.3c02794. https://www.osti.gov/servlets/purl/1998754.
@article{osti_1998754,
title = {Electronic Structure of the Complete Series of Gas-Phase Manganese Acetylacetonates by X-ray Absorption Spectroscopy},
author = {Ablyasova, Olesya S. and Guo, Meiyuan and Zamudio-Bayer, Vicente and Kubin, Markus and Gitzinger, Tim and da Silva Santos, Mayara and Flach, Max and Timm, Martin and Lundberg, Marcus and Lau, J. Tobias and Hirsch, Konstantin},
abstractNote = {Metal centers in transition metal–ligand complexes occur in a variety of oxidation states causing their redox activity and therefore making them relevant for applications in physics and chemistry. The electronic state of these complexes can be studied by X-ray absorption spectroscopy, which is, however, due to the complex spectral signature not always straightforward. Here, we study the electronic structure of gas-phase cationic manganese acetylacetonate complexes Mn(acac)1–3+ using X-ray absorption spectroscopy at the metal center and ligand constituents. The spectra are well reproduced by multiconfigurational wave function theory, time-dependent density functional theory as well as parameterized crystal field and charge transfer multiplet simulations. This enables us to get detailed insights into the electronic structure of ground-state Mn(acac)1–3+ and extract empirical parameters such as crystal field strength and exchange coupling from X-ray excitation at both the metal and ligand sites. By comparison to X-ray absorption spectra of neutral, solvated Mn(acac)2,3 complexes, we also show that the effect of coordination on the L3 excitation energy, routinely used to identify oxidation states, can contribute about 40–50% to the observed shift, which for the current study is 1.9 eV per oxidation state.},
doi = {10.1021/acs.jpca.3c02794},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 34,
volume = 127,
place = {United States},
year = {Thu Aug 17 00:00:00 EDT 2023},
month = {Thu Aug 17 00:00:00 EDT 2023}
}
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