43749
2018
2019
eng
7243
7253
11
779
postprint
1
2019-11-26
2019-11-26
--
Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species
We describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L-3-edge RIXS in the ferricyanide complex Fe(CN)(6)(3-), we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject the presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.
Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe
urn:nbn:de:kobv:517-opus4-437493
10.25932/publishup-43749
1866-8372
online registration
Physical chemistry, chemical physics 20 (2018), S. 7243–7253 DOI: 10.1039/c7cp08326b
<a href="http://publishup.uni-potsdam.de/52249">Bibliographieeintrag der Originalveröffentlichung/Quelle</a>
Jesper Norell
Raphael Martin Jay
Markus Hantschmann
Sebastian Oliver Eckert
Meiyuan Guo
Kelly J. Gaffney
Philippe Wernet
Marcus Lundberg
Alexander Föhlisch
Michael Odelius
Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe
779
eng
uncontrolled
charge-transfer
eng
uncontrolled
relaxation dynamics
eng
uncontrolled
absorption-spectra
eng
uncontrolled
energy-conversion
eng
uncontrolled
basis-sets
eng
uncontrolled
ab-initio
eng
uncontrolled
complexes
eng
uncontrolled
photoelectron
eng
uncontrolled
spectroscopy
eng
uncontrolled
simulations
Chemie und zugeordnete Wissenschaften
open_access
Mathematisch-Naturwissenschaftliche Fakultät
Referiert
Open Access
Horizon 2020
Universität Potsdam
https://publishup.uni-potsdam.de/files/43749/pmnr779.pdf
52249
2018
2018
eng
7243
7253
20
other
RSC Publ.
Cambridge
1
--
2018-02-20
--
Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft x-ray scattering in transient photo-chemical species
We describe how inversion symmetry separation of electronic state manifolds in resonant inelastic soft X-ray scattering (RIXS) can be applied to probe excited-state dynamics with compelling selectivity. In a case study of Fe L3-edge RIXS in the ferricyanide complex Fe(CN)63−, we demonstrate with multi-configurational restricted active space spectrum simulations how the information content of RIXS spectral fingerprints can be used to unambiguously separate species of different electronic configurations, spin multiplicities, and structures, with possible involvement in the decay dynamics of photo-excited ligand-to-metal charge-transfer. Specifically, we propose that this could be applied to confirm or reject the presence of a hitherto elusive transient Quartet species. Thus, RIXS offers a particular possibility to settle a recent controversy regarding the decay pathway, and we expect the technique to be similarly applicable in other model systems of photo-induced dynamics.
Physical chemistry, chemical physics
1463-9084
10.1039/c7cp08326b
wos:2018
AUG 19-23, 2018
WOS:000447609103557
Boston, MA
jesper.norell@fysik.su.se
2021-10-15T09:14:41+00:00
sword
importub
filename=package.tar
d13f7c05d293dfbca741a9cc2244aceb
Norell, Jesper
<a href="https://doi.org/10.25932/publishup-43749">Zweitveröffentlichung in der Schriftenreihe Postprints der Universität Potsdam : Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe ; 779 </a>
false
true
Jesper Norell
Raphael Jay
Markus Hantschmann
Sebastian Oliver Eckert
Meiyuan Guo
Kelly Gaffney
Philippe Wernet
Marcus Lundberg
Alexander Föhlisch
Michael Odelius
Physik
Institut für Physik und Astronomie
Referiert
Import
52015
2018
2018
eng
6813
6829
17
33
9
article
Royal Society of Chemistry
Cambridge
1
--
--
--
Probing the oxidation state of transition metal complexes
Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn-II(acac)(2) and Mn-III(acac)(3) as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn-III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.
Chemical science
a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies
10.1039/c8sc00550h
30310614
2041-6520
2041-6539
wos:2018
WOS:000443270300009
Wernet, P (reprint author), Helmholtz Zentrum Berlin Mat & Energie GmbH, Inst Methods & Instrumentat Synchrotron Radiat Re, Albert Einstein Str 15, D-12489 Berlin, Germany.; Lundberg, M (reprint author), Uppsala Univ, Dept Chem, Angstrom Lab, Uppsala, Sweden., marcus.lundberg@kemi.uu.se; wernet@helmholtz-berlin.de
Human Frontiers Science ProgramHuman Frontier Science Program [RGP0063/2013]; Swedish Research CouncilSwedish Research Council; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation [KAW-2013.0020]; DOE Office of Biological and Environmental ResearchUnited States Department of Energy (DOE); National Institutes of Health, National Institute of General Medical SciencesUnited States Department of Health & Human ServicesNational Institutes of Health (NIH) - USANIH National Institute of General Medical Sciences (NIGMS) [P41GM103393]; Helmholtz Virtual Institute "Dynamic Pathways in Multidimensional Landscapes"; Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences of the Department of Energy [DE-AC02-05CH11231]; NIHUnited States Department of Health & Human ServicesNational Institutes of Health (NIH) - USA [GM110501, GM55302]
2021-10-04T10:14:36+00:00
sword
importub
filename=package.tar
93391e063cfd49ed9053af62d5a61dcd
<a href="https://doi.org/10.25932/publishup-42505">Zweitveröffentlichung in der Schriftenreihe Postprints der Universität Potsdam : Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe ; 656 </a>
false
true
Markus Kubin
Meiyuan Guo
Thomas Kroll
Heike Loechel
Erik Kallman
Michael L. Baker
Rolf Mitzner
Sheraz Gul
Jan Kern
Alexander Föhlisch
Alexei Erko
Uwe Bergmann
Vittal Yachandra
Junko Yano
Marcus Lundberg
Philippe Wernet
Chemie und zugeordnete Wissenschaften
Institut für Mathematik
Referiert
Import
Gold Open-Access
DOAJ gelistet
42505
2018
2019
eng
17
656
postprint
1
2019-02-27
2019-02-27
--
Probing the oxidation state of transition metal complexes
Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn-II(acac)(2) and Mn-III(acac)(3) as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn-III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.
Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe
a case study on how charge and spin densities determine Mn L-edge X-ray absorption energies
10.25932/publishup-42505
urn:nbn:de:kobv:517-opus4-425057
1866-8372
online registration
Chemical Science 9 (2018), pp.6813–6829 DOI 10.1039/c8sc00550h
<a href="http://publishup.uni-potsdam.de/52015">Bibliographieeintrag der Originalveröffentlichung/Quelle</a>
CC-BY - Namensnennung 4.0 International
Markus Kubin
Meiyuan Guo
Thomas Kroll
Heike Löchel
Erik Källman
Michael L. Baker
Rolf Mitzner
Sheraz Gul
Jan Kern
Alexander Föhlisch
Alexei Erko
Uwe Bergmann
Vittal Yachandra
Junko Yano
Marcus Lundberg
Philippe Wernet
Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe
656
eng
uncontrolled
electronic-structure
eng
uncontrolled
atomic multiplet
eng
uncontrolled
water-oxidation
eng
uncontrolled
iron complexes
eng
uncontrolled
photosystem-II
eng
uncontrolled
spectroscopy
eng
uncontrolled
manganese
eng
uncontrolled
spectra
eng
uncontrolled
ligand
eng
uncontrolled
FE
Chemie und zugeordnete Wissenschaften
open_access
Mathematisch-Naturwissenschaftliche Fakultät
Referiert
Open Access
Universität Potsdam
https://publishup.uni-potsdam.de/files/42505/pmnr656.pdf