TY  - THES
A1  - Hantschmann, Markus
T1  - Stimulated resonant inelastic X-ray scattering in transition metal systems
T1  - Resonante Inelastische Röntgenstreuung in Übergangsmetall-Komplexen
N2  - With the implementation of intense, short pulsed light sources throughout the last years, the powerful technique of resonant inelastic X-ray scattering (RIXS) became feasible for a wide range of experiments within femtosecond dynamics in correlated materials and molecules. 
In this thesis I investigate the potential to bring RIXS into the fluence regime of nonlinear X-ray-matter interactions, especially focusing on the impact of stimulated scattering on RIXS in transition metal systems in a transmission spectroscopy geometry around transition metal L-edges.
After presenting the RIXS toolbox and the capabilities of free electron laser light sources for ultrafast intense X-ray experiments, the thesis explores an experiment designed to understand the impact of stimulated scattering on diffraction and direct beam transmission spectroscopy on a CoPd multilayer system. The experiments require short X-ray pulses that can only be generated at free electron lasers (FEL). Here the pulses are not only short, but also very intense, which opens the door to nonlinear X-ray-matter interactions. In the second part of this thesis, we investigate observations in the nonlinear interaction regime, look at potential difficulties for classic spectroscopy and investigate possibilities to enhance the RIXS through stimulated scattering. Here, a study on stimulated RIXS is presented, where we investigate the light field intensity dependent CoPd demagnetization in transmission as well as scattering geometry. Thereby we show the first direct observation of stimulated RIXS as well as light field induced nonlinear effects, 
namely the breakdown of scattering intensity and the increase in sample transmittance. The topic is of ongoing interest and will just increase in relevance as more free electron lasers are planned and the number of experiments at such light sources will continue to increase in the near future. 		
Finally we present a discussion on the accessibility of small DOS shifts in the absorption-band of transition metal complexes through stimulated resonant X-ray scattering. As these shifts occur for example in surface states this finding could expand the experimental selectivity of NEXAFS and RIXS to the detectability of surface states. We show how stimulation can indeed enhance the visibility of DOS shifts through the detection of stimulated spectral shifts and enhancements in this theoretical study. We also forecast the observation of stimulated enhancements in resonant excitation experiments at FEL sources in systems with a high density of states just below the Fermi edge and in systems with an occupied to unoccupied DOS ratio in the valence band above 1.
N2  - In dieser Arbeit wird die Weiterentwicklung der Technik ’Resonante Inelastische Röntgenstreuung’ (RIXS) thematisiert. Vor allem wird das Thema der nichtlinearen Röntgen-Materie-Wechselwirkung an Freien Elektronenlasern wird ausführlich diskutiert. Mit der Etablierung von intensiven kurzpulsigen
Röntgenquellen auf Basis von freien Elektronenlasern, ist die Möglichkeit entstanden, zeitaufgelöste Experimente im Femtosekundenbereich mit Röntgenstrahlung durchzuführen. Die dort erzeugten Pulse sind so intensiv und kurz, dass neue Effekte, die analogien in der nichtlinearen Optik haben, auftreten können. Diese neu auftretenden Effekte sind für die Röntgengemeinschaft vollkommen neu und müssen verstanden werden um freie Elektronenlaser sinnvoll auf größerer Skala, sinnvoll nutzen zu können. Außerdem könnten diese Effekte auch ganz neue experimentelle Möglichkeiten eröffnen. Deswegen beschäftigt sich diese Arbeit vor allem mit der potentiellen Möglichkeit, die RIXS Technik im nicht-linearen Licht-Materie Wechselwirkungsbereich zu bringen, die geänderten Interaktionen zu verstehen und vielleicht sogar nutzbar zu machen. Zu Beginn werden die Möglichkeiten der RIXS Technik vorgestellt. Im Anschluss wird ein von uns in Kollaboration mit dem SLAC entwickeltes und durchgeführtes Experiment vorgestellt, welches unter anderem die erste direkte Beobachtung von stimulierter resonanter inelastischer Röntgenbeugung an dünnen CoPd Multischichtsystemen ermöglicht hat. Außerdem sind intensitätsabhängige Veränderungen der Licht-Materie Wechselwirkung beobachtet worden. Speziell konnten wir einen klaren Zusammenhang zwischen dem Zusammenbruch von Streuintensität (entspricht etwa der Intensit¨ at, die nicht in direkter Strahlrichtung abgestrahlt wird) und der Vergrößerung der Transmittivität (Intensität, die in Strahlrichtung durch die Probe propagiert) feststellen. Dies konnte mit der Verschiebung von Auger und Streueffekten zu stimulierten Effekten verknüpft werden.
Um das Experiment besser zu verstehen wurde ein Ratengleichungsmodell entwickelt, das intensitätsabhängige Wirkungsquerschnitte inkludiert und damit intensitätsabhängige Puls-induzierte Effekte abschätzen kann. Es konnte gezeigt werden wie die Intensitätsabhängikeit von Puls-Induzierter Transparenz, Puls-induziertem zusammenbruch der Röntgenstreuung, und die Verstärkung von Teilen des Pulses mit stimulierten Emissionen verknüpft sind. Außerdem konnten einige Aspekte identifiziert werden, die dabei helfen können um neue Experimente zu designen, die in der Lage wären durch das Ausnutzen von stimulierter Emission und damit verbundenen Spektralen verschiebungen zusätzliche Informationen aus den zu untersuchenden Systemen zu gewinnen, wie zum Beispiel über die elektronische Zustandsdichte in einer Oberflächen- oder Interface-Schicht.
KW  - RIXS
KW  - free electron laser
KW  - transition metal systems
KW  - rate equation
KW  - RIXS
KW  - resonante inelastische Röntgenstreuung
KW  - Freie Elektronen Laser
KW  - Übergangsmetall - Komplexe
Y1  - 2023
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-584761
ER  - 
TY  - JOUR
A1  - Beye, Martin
A1  - Öberg, Henrik
A1  - Xin, Hongliang
A1  - Dakovski, Georgi L.
A1  - Föhlisch, Alexander
A1  - Gladh, Jorgen
A1  - Hantschmann, Markus
A1  - Hieke, Florian
A1  - Kaya, Sarp
A1  - Kühn, Danilo
A1  - LaRue, Jerry
A1  - Mercurio, Giuseppe
A1  - Minitti, Michael P.
A1  - Mitra, Ankush
A1  - Moeller, Stefan P.
A1  - Ng, May Ling
A1  - Nilsson, Anders
A1  - Nordlund, Dennis
A1  - Norskov, Jens
A1  - Öström, Henrik
A1  - Ogasawara, Hirohito
A1  - Persson, Mats
A1  - Schlotter, William F.
A1  - Sellberg, Jonas A.
A1  - Wolf, Martin
A1  - Abild-Pedersen, Frank
A1  - Pettersson, Lars G. M.
A1  - Wurth, Wilfried
T1  - Chemical Bond Activation Observed with an X-ray Laser
JF  - The journal of physical chemistry letters
N2  - The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free electron laser to directly observe the decreased bonding antibonding splitting following bond-activation using an ultrashort optical laser pulse.
Y1  - 2016
U6  - https://doi.org/10.1021/acs.jpclett.6b01543
SN  - 1948-7185
VL  - 7
SP  - 3647
EP  - 3651
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - JOUR
A1  - Ostrom, H.
A1  - Oberg, H.
A1  - Xin, H.
A1  - Larue, J.
A1  - Beye, Martin
A1  - Gladh, J.
A1  - Ng, M. L.
A1  - Sellberg, J. A.
A1  - Kaya, S.
A1  - Mercurio, G.
A1  - Nordlund, D.
A1  - Hantschmann, Markus
A1  - Hieke, F.
A1  - Kuehn, D.
A1  - Schlotter, W. F.
A1  - Dakovski, G. L.
A1  - Turner, J. J.
A1  - Minitti, M. P.
A1  - Mitra, A.
A1  - Moeller, S. P.
A1  - Föhlisch, Alexander
A1  - Wolf, M.
A1  - Wurth, W.
A1  - Persson, Mats
A1  - Norskov, J. K.
A1  - Abild-Pedersen, Frank
A1  - Ogasawara, Hirohito
A1  - Pettersson, Lars G. M.
A1  - Nilsson, A.
T1  - Probing the transition state region in catalytic CO oxidation on Ru
JF  - Science
N2  - Femtosecond x-ray laser pulses are used to probe the carbon monoxide (CO) oxidation reaction on ruthenium (Ru) initiated by an optical laser pulse. On a time scale of a few hundred femtoseconds, the optical laser pulse excites motions of CO and oxygen (O) on the surface, allowing the reactants to collide, and, with a transient close to a picosecond (ps), new electronic states appear in the OK-edge x-ray absorption spectrum. Density functional theory calculations indicate that these result from changes in the adsorption site and bond formation between CO and O with a distribution of OC-O bond lengths close to the transition state (TS). After 1 ps, 10% of the CO populate the TS region, which is consistent with predictions based on a quantum oscillator model.
Y1  - 2015
U6  - https://doi.org/10.1126/science.1261747
SN  - 0036-8075
SN  - 1095-9203
VL  - 347
IS  - 6225
SP  - 978
EP  - 982
PB  - American Assoc. for the Advancement of Science
CY  - Washington
ER  - 
TY  - JOUR
A1  - Hantschmann, Markus
A1  - Föhlisch, Alexander
T1  - A rate model approach for FEL pulse induced transmissions changes, saturable absorption, X-ray transparency and stimulated emission
JF  - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy
N2  - As the use of free electron laser (FEL) sources increases, so do the findings mentioning non-linear phenomena occurring at these experiments, such as saturable absorption, induced transparency and scattering breakdowns. These are well known among the laser community, but are still rarely understood and expected among the X-ray community and to date lack tools and theories to accurately predict the respective experimental parameters and results. We present a simple theoretical framework to access short X-ray pulse induced light- matter interactions which occur at intense short X-ray pulses as available at FEL sources. Our approach allows to investigate effects such as saturable absorption, induced transparency and scattering suppression, stimulated emission, and transmission spectra, while including the density of state influence relevant to soft X-ray spectroscopy in, for example, transition metal complexes or functional materials. This computationally efficient rate model based approach is intuitively adaptable to most solid state sample systems in the soft X-ray spectrum with the potential to be extended for liquid and gas sample systems as well. The feasibility of the model to estimate the named effects and the influence of the density of state is demonstrated using the example of CoPd transition metal systems at the Co edge. We believe this work is an important contribution for the preparation, performance, and understanding of FEL based high intensity and short pulse experiments, especially on functional materials in the soft X-ray spectrum.
KW  - Free-electron-laser science
KW  - RIXS at FELs
KW  - Stimulated scattering
KW  - Pulse induced transparency
KW  - Scattering breakdown
Y1  - 2022
U6  - https://doi.org/10.1016/j.elspec.2021.147139
SN  - 0368-2048
VL  - 256
PB  - Elsevier
CY  - Amsterdam
ER  - 
TY  - JOUR
A1  - Eckert, Sebastian
A1  - Norell, Jesper
A1  - Miedema, Piter S.
A1  - Beye, Martin
A1  - Fondell, Mattis
A1  - Quevedo, Wilson
A1  - Kennedy, Brian
A1  - Hantschmann, Markus
A1  - Pietzsch, Annette
A1  - van Kuiken, Benjamin
A1  - Ross, Matthew
A1  - Minitti, Michael P.
A1  - Moeller, Stefan P.
A1  - Schlotter, William F.
A1  - Khalil, Munira
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Untersuchung unabhängiger N‐H‐ und N‐C‐Bindungsverformungen auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung
JF  - Angewandte Chemie
N2  - Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala.
KW  - Photochemie
KW  - Protonierung
KW  - RIXS (resonante inelastische Röntgenstreuung)
KW  - Selektiver Bindungsbruch
KW  - Stickstoff
Y1  - 2017
U6  - https://doi.org/10.1002/ange.201700239
SN  - 1521-3757
SN  - 1521-3773
VL  - 129
IS  - 22
SP  - 6184
EP  - 6188
ER  - 
TY  - JOUR
A1  - Eckert, Sebastian
A1  - Norell, Jesper
A1  - Miedema, Piter S.
A1  - Beye, Martin
A1  - Fondell, Mattis
A1  - Quevedo, Wilson
A1  - Kennedy, Brian
A1  - Hantschmann, Markus
A1  - Pietzsch, Annette
A1  - Van Kuiken, Benjamin E.
A1  - Ross, Matthew
A1  - Minitti, Michael P.
A1  - Moeller, Stefan P.
A1  - Schlotter, William F.
A1  - Khalil, Munira
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering
JF  - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition
N2  - The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale.
KW  - nitrogen
KW  - photochemistry
KW  - protonation
KW  - RIXS (resonant inelastic X-ray scattering)
KW  - selective bond cleavage
Y1  - 2017
U6  - https://doi.org/10.1002/anie.201700239
SN  - 1433-7851
SN  - 1521-3773
VL  - 56
SP  - 6088
EP  - 6092
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Jay, Raphael M.
A1  - Norell, Jesper
A1  - Eckert, Sebastian
A1  - Hantschmann, Markus
A1  - Beye, Martin
A1  - Kennedy, Brian
A1  - Quevedo, Wilson
A1  - Schlotter, William F.
A1  - Dakovski, Georgi L.
A1  - Minitti, Michael P.
A1  - Hoffmann, Matthias C.
A1  - Mitra, Ankush
A1  - Moeller, Stefan P.
A1  - Nordlund, Dennis
A1  - Zhang, Wenkai
A1  - Liang, Huiyang W.
A1  - Kunnus, Kristian
A1  - Kubicek, Katharina
A1  - Techert, Simone A.
A1  - Lundberg, Marcus
A1  - Wernet, Philippe
A1  - Gaffney, Kelly
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Disentangling Transient Charge Density and Metal-Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering
JF  - The journal of physical chemistry letters
N2  - Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal-ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. pi-Back-donation is found to be mainly determined by the metal site occupation, whereas the ligand hole instead influences sigma-donation. Our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.
Y1  - 2018
U6  - https://doi.org/10.1021/acs.jpclett.8b01429
SN  - 1948-7185
VL  - 9
IS  - 12
SP  - 3538
EP  - 3543
PB  - American Chemical Society
CY  - Washington
ER  - 
TY  - GEN
A1  - Norell, Jesper
A1  - Jay, Raphael
A1  - Hantschmann, Markus
A1  - Eckert, Sebastian
A1  - Guo, Meiyuan
A1  - Gaffney, Kelly
A1  - Wernet, Philippe
A1  - Lundberg, Marcus
A1  - Föhlisch, Alexander
A1  - Odelius, Michael
T1  - Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft x-ray scattering in transient photo-chemical species
T2  - Physical chemistry, chemical physics
N2  - 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.
Y1  - 2018
U6  - https://doi.org/10.1039/c7cp08326b
SN  - 1463-9084
IS  - 20
SP  - 7243
EP  - 7253
PB  - RSC Publ.
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Eckert, Sebastian
A1  - Beye, Martin
A1  - Pietzsch, Annette
A1  - Quevedo, Wilson
A1  - Hantschmann, Markus
A1  - Ochmann, Miguel
A1  - Ross, Matthew
A1  - Minitti, Michael P.
A1  - Turner, Joshua J.
A1  - Moeller, Stefan P.
A1  - Schlotter, William F.
A1  - Dakovski, Georgi L.
A1  - Khalil, Munira
A1  - Huse, Nils
A1  - Föhlisch, Alexander
T1  - Principles of femtosecond X-ray/optical cross-correlation with X-ray induced transient optical reflectivity in solids
JF  - Applied physics letters
N2  - The discovery of ultrafast X-ray induced optical reflectivity changes enabled the development of X-ray/optical cross correlation techniques at X-ray free electron lasers worldwide. We have now linked through experiment and theory the fundamental excitation and relaxation steps with the transient optical properties in finite solid samples. Therefore, we gain a thorough interpretation and an optimized detection scheme of X-ray induced changes to the refractive index and the X-ray/optical cross correlation response. (C) 2015 AIP Publishing LLC.
Y1  - 2015
U6  - https://doi.org/10.1063/1.4907949
SN  - 0003-6951
SN  - 1077-3118
VL  - 106
IS  - 6
PB  - American Institute of Physics
CY  - Melville
ER  - 
TY  - GEN
A1  - Eckert, Sebastian
A1  - Norell, Jesper
A1  - Miedema, Piter S.
A1  - Beye, Martin
A1  - Fondell, Mattis
A1  - Quevedo, Wilson
A1  - Kennedy, Brian
A1  - Hantschmann, Markus
A1  - Pietzsch, Annette
A1  - van Kuiken, Benjamin E.
A1  - Ross, Matthew
A1  - Minitti, Michael P.
A1  - Moeller, Stefan P.
A1  - Schlotter, William F.
A1  - Khalil, Munira
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Untersuchung unabhängiger N‐H‐ und N‐C‐Bindungsverformungen auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung
T2  - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe
N2  - Die Femtosekundendynamik nach resonanten Photoanregungen mit optischen und Röntgenpulsen ermöglicht eine selektive Verformung von chemischen N‐H‐ und N‐C‐Bindungen in 2‐Thiopyridon in wässriger Lösung. Die Untersuchung der orbitalspezifischen elektronischen Struktur und ihrer Dynamik auf ultrakurzen Zeitskalen mit resonanter inelastischer Röntgenstreuung an der N1s‐Resonanz am Synchrotron und dem Freie‐Elektronen‐Laser LCLS in Kombination mit quantenchemischen Multikonfigurationsberechnungen erbringen den direkten Nachweis dieser kontrollierten photoinduzierten Molekülverformungen und ihrer ultrakurzen Zeitskala.
T3  - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1121 
KW  - Photochemie
KW  - Protonierung
KW  - RIXS (resonante inelastische Röntgenstreuung)
KW  - Selektiver Bindungsbruch
KW  - Stickstoff
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-436688
SN  - 1866-8372
IS  - 1121
ER  - 
TY  - GEN
A1  - Eckert, Sebastian
A1  - Norell, Jesper
A1  - Miedema, Piter S.
A1  - Beye, Martin
A1  - Fondell, Mattis
A1  - Quevedo, Wilson
A1  - Kennedy, Brian
A1  - Hantschmann, Markus
A1  - Pietzsch, Annette
A1  - van Kuiken, Benjamin E.
A1  - Ross, Matthew
A1  - Minitti, Michael P.
A1  - Moeller, Stefan P.
A1  - Schlotter, William F.
A1  - Khalil, Munira
A1  - Odelius, Michael
A1  - Föhlisch, Alexander
T1  - Ultrafast Independent N-H and N-C Bond Deformation Investigated with Resonant Inelastic X-Ray Scattering
T2  - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe
N2  - The femtosecond excited-state dynamics following resonant photoexcitation enable the selective deformation of N-H and N-C chemical bonds in 2-thiopyridone in aqueous solution with optical or X-ray pulses. In combination with multiconfigurational quantum-chemical calculations, the orbital-specific electronic structure and its ultrafast dynamics accessed with resonant inelastic X-ray scattering at the N 1s level using synchrotron radiation and the soft X-ray free-electron laser LCLS provide direct evidence for this controlled photoinduced molecular deformation and its ultrashort time-scale.
T3  - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1115 
KW  - nitrogen
KW  - photochemistry
KW  - protonation
KW  - RIXS (resonant inelastic X-ray scattering)
KW  - selective bond cleavage
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-436873
SN  - 1866-8372
IS  - 1115
ER  - 
TY  - GEN
A1  - Norell, Jesper
A1  - Jay, Raphael Martin
A1  - Hantschmann, Markus
A1  - Eckert, Sebastian
A1  - Guo, Meiyuan
A1  - Gaffney, Kelly J.
A1  - Wernet, Philippe
A1  - Lundberg, Marcus
A1  - Föhlisch, Alexander
A1  - Odelius, Michael
T1  - Fingerprints of electronic, spin and structural dynamics from resonant inelastic soft X-ray scattering in transient photo-chemical species
T2  - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe
N2  - 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.
T3  - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 779 
KW  - charge-transfer
KW  - relaxation dynamics
KW  - absorption-spectra
KW  - energy-conversion
KW  - basis-sets
KW  - ab-initio
KW  - complexes
KW  - photoelectron
KW  - spectroscopy
KW  - simulations
Y1  - 2019
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-437493
SN  - 1866-8372
IS  - 779
SP  - 7243
EP  - 7253
ER  -