Stimulated x-ray emission spectroscopy in transition metal complexes
Abstract
We report the observation and analysis of the gain curve of amplified Kα x-ray emission from solutions of Mn(II) and Mn(VII) complexes using an x-ray free electron laser to create the 1s core-hole population inversion. We find spectra at amplification levels extending over 4 orders of magnitude until saturation. We observe bandwidths below the Mn 1s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ~1.7 eV FWHM is constant over 3 orders of magnitude, pointing to the buildup of transform limited pulses of ~1 fs duration. Driving the amplification into saturation leads to broadening and a shift of the line. Importantly, the chemical sensitivity of the stimulated x-ray emission to the Mn oxidation state is preserved at power densities of ~1020 W/cm2 for the incoming x-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) x-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear x-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis, and materials science.
- Authors:
-
more »
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS) and Stanford Synchrotron Radiation Lightsource (SSRL)
- Max Planck Inst. for the Structure and Dynamics of Matter, Hamburg (Germany); SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
- Max Planck Inst. for the Structure and Dynamics of Matter, Hamburg (Germany)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Accelerator Directorate
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
- Max Planck Inst. for the Structure and Dynamics of Matter, Hamburg (Germany); Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany); Univ. of Hamburg, Hamburg (Germany)
- SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS); SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Laboratory Directed Research and Development (LDRD) Program; National Institutes of Health (NIH)
- OSTI Identifier:
- 1421553
- Alternate Identifier(s):
- OSTI ID: 1429943; OSTI ID: 1465454
- Grant/Contract Number:
- AC02-76SF00515; AC02-05CH11231; GM055302; GM110501; F32GM116423; RGP0063/2013 310
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review Letters
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 13; Journal ID: ISSN 0031-9007
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; 72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS
Citation Formats
Kroll, Thomas, Weninger, Clemens, Alonso-Mori, Roberto, Sokaras, Dimosthenis, Zhu, Diling, Mercadier, Laurent, Majety, Vinay P., Marinelli, Agostino, Lutman, Alberto, Guetg, Marc, Decker, Franz-Josef, Boutet, Sebastien, Aquila, Andy, Koglin, Jason, Koralek, Jake, DePonte, Daniel P., Kern, Jan, Fuller, Franklin D., Pastor, Ernest, Fransson, Thomas, Zhang, Yu, Yano, Junko, Yachandra, Vittal K., Rohringer, Nina, and Bergmann, Uwe. Stimulated x-ray emission spectroscopy in transition metal complexes. United States: N. p., 2018.
Web. doi:10.1103/PhysRevLett.120.133203.
Kroll, Thomas, Weninger, Clemens, Alonso-Mori, Roberto, Sokaras, Dimosthenis, Zhu, Diling, Mercadier, Laurent, Majety, Vinay P., Marinelli, Agostino, Lutman, Alberto, Guetg, Marc, Decker, Franz-Josef, Boutet, Sebastien, Aquila, Andy, Koglin, Jason, Koralek, Jake, DePonte, Daniel P., Kern, Jan, Fuller, Franklin D., Pastor, Ernest, Fransson, Thomas, Zhang, Yu, Yano, Junko, Yachandra, Vittal K., Rohringer, Nina, & Bergmann, Uwe. Stimulated x-ray emission spectroscopy in transition metal complexes. United States. https://doi.org/10.1103/PhysRevLett.120.133203
Kroll, Thomas, Weninger, Clemens, Alonso-Mori, Roberto, Sokaras, Dimosthenis, Zhu, Diling, Mercadier, Laurent, Majety, Vinay P., Marinelli, Agostino, Lutman, Alberto, Guetg, Marc, Decker, Franz-Josef, Boutet, Sebastien, Aquila, Andy, Koglin, Jason, Koralek, Jake, DePonte, Daniel P., Kern, Jan, Fuller, Franklin D., Pastor, Ernest, Fransson, Thomas, Zhang, Yu, Yano, Junko, Yachandra, Vittal K., Rohringer, Nina, and Bergmann, Uwe. Tue .
"Stimulated x-ray emission spectroscopy in transition metal complexes". United States. https://doi.org/10.1103/PhysRevLett.120.133203. https://www.osti.gov/servlets/purl/1421553.
@article{osti_1421553,
title = {Stimulated x-ray emission spectroscopy in transition metal complexes},
author = {Kroll, Thomas and Weninger, Clemens and Alonso-Mori, Roberto and Sokaras, Dimosthenis and Zhu, Diling and Mercadier, Laurent and Majety, Vinay P. and Marinelli, Agostino and Lutman, Alberto and Guetg, Marc and Decker, Franz-Josef and Boutet, Sebastien and Aquila, Andy and Koglin, Jason and Koralek, Jake and DePonte, Daniel P. and Kern, Jan and Fuller, Franklin D. and Pastor, Ernest and Fransson, Thomas and Zhang, Yu and Yano, Junko and Yachandra, Vittal K. and Rohringer, Nina and Bergmann, Uwe},
abstractNote = {We report the observation and analysis of the gain curve of amplified Kα x-ray emission from solutions of Mn(II) and Mn(VII) complexes using an x-ray free electron laser to create the 1s core-hole population inversion. We find spectra at amplification levels extending over 4 orders of magnitude until saturation. We observe bandwidths below the Mn 1s core-hole lifetime broadening in the onset of the stimulated emission. In the exponential amplification regime the resolution corrected spectral width of ~1.7 eV FWHM is constant over 3 orders of magnitude, pointing to the buildup of transform limited pulses of ~1 fs duration. Driving the amplification into saturation leads to broadening and a shift of the line. Importantly, the chemical sensitivity of the stimulated x-ray emission to the Mn oxidation state is preserved at power densities of ~1020 W/cm2 for the incoming x-ray pulses. Differences in signal sensitivity and spectral information compared to conventional (spontaneous) x-ray emission spectroscopy are discussed. Our findings build a baseline for nonlinear x-ray spectroscopy for a wide range of transition metal complexes in inorganic chemistry, catalysis, and materials science.},
doi = {10.1103/PhysRevLett.120.133203},
journal = {Physical Review Letters},
number = 13,
volume = 120,
place = {United States},
year = {Tue Mar 27 00:00:00 EDT 2018},
month = {Tue Mar 27 00:00:00 EDT 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 38 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Temperature- and pressure-induced spin-state transitions in
journal, January 2006
- Vankó, György; Rueff, Jean-Pascal; Mattila, Aleksi
- Physical Review B, Vol. 73, Issue 2
Quantum theory of a swept-gain laser amplifier
journal, December 1975
- Hopf, Frederic A.; Meystre, Pierre
- Physical Review A, Vol. 12, Issue 6
Atomic inner-shell laser at 1.5-ångström wavelength pumped by an X-ray free-electron laser
journal, August 2015
- Yoneda, Hitoki; Inubushi, Yuichi; Nagamine, Kazunori
- Nature, Vol. 524, Issue 7566
Tracking excited-state charge and spin dynamics in iron coordination complexes
journal, May 2014
- Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe
- Nature, Vol. 509, Issue 7500
Natural widths of atomic K and L levels, K α X‐ray lines and several K L L Auger lines
journal, April 1979
- Krause, M. O.; Oliver, J. H.
- Journal of Physical and Chemical Reference Data, Vol. 8, Issue 2
X-ray emission spectroscopy
journal, August 2009
- Bergmann, Uwe; Glatzel, Pieter
- Photosynthesis Research, Vol. 102, Issue 2-3
Transient-gain photoionization x-ray laser
journal, December 2014
- Weninger, Clemens; Rohringer, Nina
- Physical Review A, Vol. 90, Issue 6
Coherent control of long-range photoinduced electron transfer by stimulated X-ray Raman processes
journal, August 2016
- Dorfman, Konstantin E.; Zhang, Yu; Mukamel, Shaul
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 36
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information
journal, January 2005
- Glatzel, Pieter; Bergmann, Uwe
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
3d x-ray-absorption lines and the 3 4 multiplets of the lanthanides
journal, October 1985
- Thole, B. T.; van der Laan, G.; Fuggle, J. C.
- Physical Review B, Vol. 32, Issue 8
Coherent X-Ray Raman Spectroscopy: A Nonlinear Local Probe for Electronic Excitations
journal, July 2002
- Tanaka, Satoshi; Mukamel, Shaul
- Physical Review Letters, Vol. 89, Issue 4
Stimulated X-ray emission for materials science
journal, August 2013
- Beye, M.; Schreck, S.; Sorgenfrei, F.
- Nature, Vol. 501, Issue 7466
Steady-state pulses in a laser amplifier with a delayed swept gain
journal, January 1982
- Hopf, Frederic A.
- Optics Letters, Vol. 7, Issue 12
The Coherent X-ray Imaging instrument at the Linac Coherent Light Source
journal, April 2015
- Liang, Mengning; Williams, Garth J.; Messerschmidt, Marc
- Journal of Synchrotron Radiation, Vol. 22, Issue 3
Focal Spot and Wavefront Sensing of an X-Ray Free Electron laser using Ronchi shearing interferometry
journal, October 2017
- Nagler, Bob; Aquila, Andrew; Boutet, Sébastien
- Scientific Reports, Vol. 7, Issue 1
A compact X-ray free-electron laser emitting in the sub-ångström region
journal, June 2012
- Ishikawa, Tetsuya; Aoyagi, Hideki; Asaka, Takao
- Nature Photonics, Vol. 6, Issue 8
Ultra-efficient ionization of heavy atoms by intense X-ray free-electron laser pulses
journal, November 2012
- Rudek, Benedikt; Son, Sang-Kil; Foucar, Lutz
- Nature Photonics, Vol. 6, Issue 12
First lasing and operation of an ångstrom-wavelength free-electron laser
journal, August 2010
- Emma, P.; Akre, R.; Arthur, J.
- Nature Photonics, Vol. 4, Issue 9
Generation of subterawatt-attosecond pulses in a soft x-ray free-electron laser
journal, August 2016
- Huang, Senlin; Ding, Yuantao; Huang, Zhirong
- Physical Review Accelerators and Beams, Vol. 19, Issue 8
Amplified X-Ray Emission from Core-Ionized Diatomic Molecules
journal, January 2013
- Kimberg, Victor; Rohringer, Nina
- Physical Review Letters, Vol. 110, Issue 4
Generation of High-Power High-Intensity Short X-Ray Free-Electron-Laser Pulses
journal, January 2018
- Guetg, Marc W.; Lutman, Alberto A.; Ding, Yuantao
- Physical Review Letters, Vol. 120, Issue 1
CSPAD-140k: A versatile detector for LCLS experiments
journal, August 2013
- Herrmann, Sven; Boutet, Sébastien; Duda, Brian
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 718
Femtosecond electronic response of atoms to ultra-intense X-rays
journal, July 2010
- Young, L.; Kanter, E. P.; Krässig, B.
- Nature, Vol. 466, Issue 7302
Monitoring Long-Range Electron Transfer Pathways in Proteins by Stimulated Attosecond Broadband X-ray Raman Spectroscopy
journal, October 2014
- Zhang, Yu; Biggs, Jason D.; Govind, Niranjan
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 21
Atomic inner-shell x-ray laser pumped by an x-ray free-electron laser
journal, July 2009
- Rohringer, Nina; London, Richard
- Physical Review A, Vol. 80, Issue 1
Experimental Demonstration of Femtosecond Two-Color X-Ray Free-Electron Lasers
journal, March 2013
- Lutman, A. A.; Coffee, R.; Ding, Y.
- Physical Review Letters, Vol. 110, Issue 13
Some Approaches to Vacuum uv and X‐Ray Lasers
journal, June 1967
- Duguay, M. A.; Rentzepis, P. M.
- Applied Physics Letters, Vol. 10, Issue 12
Atomic inner-shell X-ray laser at 1.46 nanometres pumped by an X-ray free-electron laser
journal, January 2012
- Rohringer, Nina; Ryan, Duncan; London, Richard A.
- Nature, Vol. 481, Issue 7382
Multidimensional resonant nonlinear spectroscopy with coherent broadband x-ray pulses
journal, March 2016
- Bennett, Kochise; Zhang, Yu; Kowalewski, Markus
- Physica Scripta, Vol. T169
Multidimensional Attosecond Resonant X-Ray Spectroscopy of Molecules: Lessons from the Optical Regime
journal, April 2013
- Mukamel, Shaul; Healion, Daniel; Zhang, Yu
- Annual Review of Physical Chemistry, Vol. 64, Issue 1
Analysis of statistical correlations and intensity spiking in the self-amplified spontaneous-emission free-electron laser
journal, May 2003
- Krinsky, S.; Gluckstern, R. L.
- Physical Review Special Topics - Accelerators and Beams, Vol. 6, Issue 5
Stochastic stimulated electronic x-ray Raman spectroscopy
journal, February 2016
- Kimberg, Victor; Rohringer, Nina
- Structural Dynamics, Vol. 3, Issue 3
A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource
journal, May 2013
- Sokaras, D.; Weng, T. -C.; Nordlund, D.
- Review of Scientific Instruments, Vol. 84, Issue 5
Stimulated Electronic X-Ray Raman Scattering
journal, December 2013
- Weninger, Clemens; Purvis, Michael; Ryan, Duncan
- Physical Review Letters, Vol. 111, Issue 23
Stimulated X-ray Raman scattering – a critical assessment of the building block of nonlinear X-ray spectroscopy
journal, January 2016
- Kimberg, Victor; Sanchez-Gonzalez, Alvaro; Mercadier, Laurent
- Faraday Discussions, Vol. 194
Analysis of a soft-x-ray laser with charge-exchange excitation
journal, March 1975
- Louisell, William H.; Scully, Marlan O.; McKnight, William B.
- Physical Review A, Vol. 11, Issue 3
X-ray nonlinear optical processes using a self-amplified spontaneous emission free-electron laser
journal, September 2007
- Rohringer, Nina; Santra, Robin
- Physical Review A, Vol. 76, Issue 3
The Theory of Atomic Structure and Spectra
book, December 1981
- Cowan, Robert D.
- Los Alamos Series in Basic and Applied Sciences, Vol. 3
Stimulated x-ray Raman Scattering – a critical assessment of the building block of nonlinear x-ray spectroscopy
text, January 2016
- Kimberg, Victor; Sanchez-Gonzalez, Alvaro; Mercadier, Laurent
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Stimulated X-ray emission for materials science
text, January 2013
- Beye, M.; Schreck, S.; Sorgenfrei, F.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Works referencing / citing this record:
Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory
journal, October 2019
- Zhang, Yu; Bergmann, Uwe; Schoenlein, Robert
- The Journal of Chemical Physics, Vol. 151, Issue 14
X-ray Raman scattering: a building block for nonlinear spectroscopy
journal, April 2019
- Rohringer, Nina
- Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2145
X-ray emission from layered media irradiated by an x-ray free-electron laser
journal, January 2020
- Peyrusse, O.; Jonnard, P.; Le Guen, K.
- Physical Review A, Vol. 101, Issue 1
Amplified spontaneous emission in the extreme ultraviolet by expanding xenon clusters
journal, June 2020
- Benediktovitch, Andrei; Mercadier, Laurent; Peyrusse, Olivier
- Physical Review A, Vol. 101, Issue 6
Violation of centrosymmetry in time-resolved coherent x-ray diffraction from rovibrational states of diatomic molecules
journal, March 2019
- Shao, Hua-Chieh; Starace, Anthony F.
- Physical Review A, Vol. 99, Issue 3
Quantum theory of superfluorescence based on two-point correlation functions
text, January 2019
- Benediktovitch, Andrei; Majety, Vinay P.; Rohringer, Nina
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Ultrafast Self-Induced X-Ray Transparency and Loss of Magnetic Diffraction
text, January 2018
- Chen, Z.; Higley, D. J.; Beye, M.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Evidence of Extreme Ultraviolet Superfluorescence in Xenon
text, January 2019
- Mercadier, L.; Benediktovitch, A.; Weninger, C.
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Amplified spontaneous emission in the extreme ultraviolet by expanding xenon clusters
text, January 2020
- Benediktovitch, Andrei; Mercadier, Laurent; Peyrusse, Olivier
- Deutsches Elektronen-Synchrotron, DESY, Hamburg
Quantum theory of superfluorescence based on two-point correlation functions
text, January 2018
- Benediktovitch, Andrei; Majety, Vinay P.; Rohringer, Nina
- arXiv