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Title: Time-dependent nonequilibrium soft x-ray response during a spin crossover

Abstract

Here, the rapid development of high-brilliance pulsed X-ray sources with femtosecond time resolution has created a need for a better theoretical understanding of the time-dependent soft-X-ray response of dissipative many-body quantum systems. It is demonstrated how soft-X-ray spectroscopies, such as X-ray absorption and resonant inelastic X-ray scattering at transition-metal L-edges, can provide insight into intersystem crossings, such as a spin crossover. The photoinduced doublet-to-quartet spin crossover on cobalt in Fe-Co Prussian blue analogues is used as an example to demonstrate how the X-ray response is affected by the dissipative nonequilibrium dynamics. The time-dependent soft-X-ray spectra provide a wealth of information that reflect the changes in the nonequilibrium initial state via continuously changing spectral lineshapes that cannot be decomposed into initial photoexcited and final metastable spectra, strong broadenings, a collapse of clear selection rules during the intersystem crossing, strong fluctuations in the isotropic branching ratio in X-ray absorption, and crystal-field collapse/oscillations and strongly time-dependent anti-Stokes processes in RIXS.

Authors:
 [1]
+ Show Author Affiliations
  1. Northern Illinois Univ., DeKalb, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1431228
Alternate Identifier(s):
OSTI ID: 1424814
Grant/Contract Number:  
AC02-06CH11357; FG02-03ER46097
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 97; Journal Issue: 12; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS

Citation Formats

van Veenendaal, Michel. Time-dependent nonequilibrium soft x-ray response during a spin crossover. United States: N. p., 2018. Web. doi:10.1103/physrevb.97.125108.
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van Veenendaal, Michel. Time-dependent nonequilibrium soft x-ray response during a spin crossover. United States. https://doi.org/10.1103/physrevb.97.125108
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van Veenendaal, Michel. Thu . "Time-dependent nonequilibrium soft x-ray response during a spin crossover". United States. https://doi.org/10.1103/physrevb.97.125108. https://www.osti.gov/servlets/purl/1431228.
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@article{osti_1431228,
title = {Time-dependent nonequilibrium soft x-ray response during a spin crossover},
author = {van Veenendaal, Michel},
abstractNote = {Here, the rapid development of high-brilliance pulsed X-ray sources with femtosecond time resolution has created a need for a better theoretical understanding of the time-dependent soft-X-ray response of dissipative many-body quantum systems. It is demonstrated how soft-X-ray spectroscopies, such as X-ray absorption and resonant inelastic X-ray scattering at transition-metal L-edges, can provide insight into intersystem crossings, such as a spin crossover. The photoinduced doublet-to-quartet spin crossover on cobalt in Fe-Co Prussian blue analogues is used as an example to demonstrate how the X-ray response is affected by the dissipative nonequilibrium dynamics. The time-dependent soft-X-ray spectra provide a wealth of information that reflect the changes in the nonequilibrium initial state via continuously changing spectral lineshapes that cannot be decomposed into initial photoexcited and final metastable spectra, strong broadenings, a collapse of clear selection rules during the intersystem crossing, strong fluctuations in the isotropic branching ratio in X-ray absorption, and crystal-field collapse/oscillations and strongly time-dependent anti-Stokes processes in RIXS.},
doi = {10.1103/physrevb.97.125108},
journal = {Physical Review B},
number = 12,
volume = 97,
place = {United States},
year = {Thu Mar 08 00:00:00 EST 2018},
month = {Thu Mar 08 00:00:00 EST 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1103/physrevb.97.125108
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Figures / Tables:

Figure 1 Figure 1: (a) Schematic description of the spin crossover in Fe-Co Prussian blue analogues. The doublet-to-quartet intersystem crossing is initiated by a Fe to Co photoexcitation. (b) The schematic energy landscape by treating the breathing mode as classical. The energies are plotted as a function of the change in metal-ligandmore » distance, where ${\Delta}{d}_{0}$ is the change in distance between the lowest states of Co3+ (low spin) and Co2+ (high spin). The red and blue energy curves indicate two- and four-fold degenerate states, respectively. The black line gives the total energy of the system (kinetic plus potential) as a function of the expectation value of the metal-ligand distance ${\langle}{\Delta}{d}{(t)} {\rangle} / {\Delta}{d}_{0}$. The numbers indicate times in femtoseconds for which the X-ray response is shown.« less
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    Works referencing / citing this record:

    Dissipation and dynamics in ultrafast intersystem crossings
    journal, January 2020

    • van Veenendaal, Michel
    • The Journal of Chemical Physics, Vol. 152, Issue 2
    • DOI: 10.1063/1.5125005
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