Format

Send to

Choose Destination
J Phys Chem Lett. 2019 Feb 7;10(3):441-446. doi: 10.1021/acs.jpclett.8b03595. Epub 2019 Jan 16.

X-ray Emission Spectroscopy at X-ray Free Electron Lasers: Limits to Observation of the Classical Spectroscopic Response for Electronic Structure Analysis.

Author information

1
Department of Physics and Astronomy , Purdue University , West Lafayette , Indiana 47907 , United States.
2
Biodesign Institute , Center for Applied Structural Discovery, Arizona State University , 85287-5301 , United States.
3
Center for Free-Electron Laser Science , Deutsches Elektronen-Synchrotron , D-22607 Hamburg , Germany.
4
The Hamburg Center for Ultrafast Imaging , Universität Hamburg , 22761 Hamburg , Germany.
5
Deutsches Elektronen-Synchrotron , D-22607 Hamburg , Germany.
6
Paul Sherrer Institut (PSI) , 5232 Villigen , Switzerland.
7
European XFEL GmbH , D-22671 Hamburg , Germany.
8
Department of Physics , Universität Hamburg , 22761 Hamburg , Germany.
9
Lawrence Livermore National Laboratory , Livermore , California 94550 , United States.
10
Hauptman-Woodward Institute, Department of Structural Biology, Jacobs School of Medicine and Biomedical Sciences , SUNY University at Buffalo , Buffalo , New York 14203 , United States.
11
BioXFEL Science and Technology Center , Buffalo , New York 14203 , United States.
12
Max Planck Institute of Biochemistry , 82152 Planegg , Germany.
13
SLAC National Accelerator Laboratory , Menlo Park , California 94025 , United States.
14
School of Molecular Sciences , Arizona State University , Tempe , Arizona 85287-1604 , United States.
15
Department of Physics , Arizona State University , Tempe , Arizona 85287-7401 , United States.
16
Department of Physics , University of Wisconsin-Milwaukee , Milwaukee , Wisconsin 53201 , United States.
17
Beijing Computational Science Research Center , Beijing 100193 , China.
18
Department of Biochemistry , University of California Davis , Davis , California 95616 , United States.
19
Max-Planck Institute for the Structure and Dynamics of Matter , D-22761 Hamburg , Germany.
20
Department of Physics , University of Washington , Seattle , Washington 98195-1560 , United States.

Abstract

X-ray free electron lasers (XFELs) provide ultrashort intense X-ray pulses suitable to probe electron dynamics but can also induce a multitude of nonlinear excitation processes. These affect spectroscopic measurements and interpretation, particularly for upcoming brighter XFELs. Here we identify and discuss the limits to observing classical spectroscopy, where only one photon is absorbed per atom for a Mn2+ in a light element (O, C, H) environment. X-ray emission spectroscopy (XES) with different incident photon energies, pulse intensities, and pulse durations is presented. A rate equation model based on sequential ionization and relaxation events is used to calculate populations of multiply ionized states during a single pulse and to explain the observed X-ray induced spectral lines shifts. This model provides easy estimation of spectral shifts, which is essential for experimental designs at XFELs and illustrates that shorter X-ray pulses will not overcome sequential ionization but can reduce electron cascade effects.

Supplemental Content

Full text links

Icon for American Chemical Society
Loading ...
Support Center