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Ultrafast photochemistry and photophysics at FXE by femtosecond spectroscopy and scattering
Dmitry Khakhulin FXE group, European XFEL
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Hard x-rays (3 – 25 keV) SASE 1 & SASE2 (Coherent) diffraction (Coherent) imaging X-ray spectroscopy
Soft x-rays (0.26 – 3 keV) SASE 3 Coherent imaging Particle & X-ray spectroscopy
XFEL photon beamlines and instruments
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Tracking ultrafast coupled electron and structural dynamics induced by light
2. Fs X-ray pulse takes a snapshot
1. Fs laser pulse triggers an ultrafast process
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Tracking ultrafast coupled electron and structural dynamics induced by light
[Fe(bpy)3]2+ (bpy = bipyridine)
W. Gawelda, et al., PRL 98 (2007)
C. Bressler, et al., Science 323 (2009)
W. Zhang, et al., Nature 509 (2014)
H.T. Lemke, et al., Nature Comm. 8 (2017)
K. S. Kjær, et al., Chemical Science 10 (2019)
….
Spin state changes
Charge transfer states
Molecular structure and solvation changes
MC states
2. Fs X-ray pulse takes a snapshot
1. Fs laser pulse triggers an ultrafast process
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
FXE: Towards a High-Speed femtosecond Molecular Camera
LPD
Johann spectrometer
Robot arm
Von Hamos spectrometer
Sample mounting stage (10 axis)
Fine sample stage (3 axis)
Flexible liquid sample support
A Suite of Simultaneous X-Ray Tools :
Single-shot dispersive non-resonant XES: von Hamos
Wide(Small)-angle X-ray Scattering and X-ray Diffraction: LPD and Jungfrau X-ray absorption spectroscopy (5-20 keV): scanning (Si(111) 4-bounce mono)
and single-shot (Spectrum analyzer)
Scanning non-resonant and resonant XES (RXES): Johann spectrometer
“Scientific instrument Femtosecond X-ray Experiments (FXE): instrumentation and baseline experimental capabilities” A. Galler et al., J. Synch. Rad., 26, 1432 (2019)
WAXS/XRD
XES
Diode
XFEL beam
Optical laser beam
XAS ∆t
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
1. Femtosecond X-ray absorption spectroscopy
Multiple scattering + bound-bound
transitions XANES
Constructive + destructive interference
J. K. Kowalska, et al., Isr. J. Chem., 803, 56, (2016)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
1. Femtosecond X-ray absorption spectroscopy
Multiple scattering + bound-bound
transitions XANES
Constructive + destructive interference
H.T. Lemke et al., Nature Comm. 8 (2017)
[Fe(bpy)3]2+ (bpy = bipyridine)
J. K. Kowalska, et al., Isr. J. Chem., 803, 56, (2016)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Scanning X-ray absorption spectroscopy at FXE: 4-bounce mono, under commissioning
Iron foil scan: FXE vs literature data
100 eV
fixed undulator gap
[Fe(terpy)2]2+ solution
XANES (TFY/HERFD)
and
EXAFS opportunities
A. Britz et al., Phys. Chem. Chem. Phys. (2020)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Single-shot dispersive X-ray absorption spectroscopy Single-shot measurements require 2 Spectrum Analyzers (SA) Pink beam would provide up to 1% bandwidth (Entire XANES spectrum @ time delay) /shot Self-normalization! Requires a fast readout gated 1D detector (Gotthard)
Y. Obara et al., Optics Express 22 (2014)
SpA-0
SpA-1
C
D. Zhu et al., APL 101 (2012)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Single-shot dispersive X-ray absorption spectroscopy
SpA-0
SpA-1
C
Single-shots @564 kHz detector (Gotthard) frame rate 10 trains, 30 pulses each
D. Zhu et al., APL 101 (2012)
Single-shot measurements require 2 Spectrum Analyzers (SA) Pink beam would provide up to 1% bandwidth (Entire XANES spectrum @ time delay) /shot Self-normalization! Requires a fast readout gated 1D detector (Gotthard)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Potential for 2D spectroscopy using stochastic X-ray pulses
Y. Kayser et al., Nat. Comm., 4761, 10, (2019)
SpA-0
SpA-1
C
RXES map
Von Hamos XES
Johann XES
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
2. Femtosecond X-ray emission spectroscopy
W. Zhang et al., Nature, 509 (2014) 345
Kβ emission on [Fe(bpy)3]2+
J. K. Kowalska, et al., Isr. J. Chem., 803, 56, (2016)
XAS XES
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
2. Femtosecond X-ray emission spectroscopy
Pump-probe Valence-to-core XES
A.M. March et al., J. Phys. Chem. B, (2017)
W. Zhang et al., Nature, 509 (2014) 345
Kβ emission on [Fe(bpy)3]2+
J. K. Kowalska, et al., Isr. J. Chem., 803, 56, (2016)
XAS XES
[Fe(terpy)2]2+
Probing valence orbitals: similar to valence band XPS, but 1) element-specific 2) no UHV requirement 3) bulk sensitive
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Femtosecond X-ray emission spectroscopy at FXE
Ambient conditions (or He atm.) offering 10 degrees of freedom, including 2 independent rotations for Johann and von Hamos spectrometers: x – translation perpendicular to x-ray beam Lower 2-theta rotation (Johann) Upper 2-theta rotation (von Hamos) Lower vertical (y) translation Theta rotation Phi and Chi rotations x, z crossed translations Upper vertical (y) translation
Johann von Hamos
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Von Hamos XES at FXE: simultaneous single-shot detection of multiple emission lines
8 x Si(531) 8 x Ge(110)
~ 77 mm
Jungfrau detector
Fe Kα Fe Kβ
Fe Kβ spectra before overlapping
Fe Kβ spectrum
Kβ
Kα
16-crystal spectrometer
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Simultaneous Ni Kα (2p 1s), Kβ (3p 1s) and VtC (valence orbitals 1s) XES! Note the intensity differs by 3 orders of magnitude.
Sample: Ni foil Beam: 9.3 keV 830 μJ/ pulse 200 pulses / train Only 10 min of data collection
Von Hamos XES at FXE: simultaneous single-shot detection of multiple emission lines 16-crystal spectrometer
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
blue: FXE (in the Rowland circle) black: data from DELTA synchrotron
Scanning-type Johann XES at FXE: 5-crystal spectrometer One crystal spectra from FXE
Co Kβ1,3 mainline
Co Kβ1,3 mainline
Co Kβ2,5 Valence-to-core
P. Glatzel et al., Sync. Rad. News, 12 (2009)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
3. Differential solution scattering – decorrelating the solute and the solvent observables
∆S (Q, t) = ∆Ssolute(Q, t) + ∆Scage(Q, t) +
∆⋅
∂∂
+∆⋅∂
∂ )()()()( tQStTT
QS solvsolv ρρ
solvent
ESRF – 25.2 keV High resolution scattering
Aqueous [Fe(bpy)3]2+
D. Khakhulin et al. Phys. Chem. Chem. Phys., 21, 9277 (2019)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Direct structural sensitivity to the solute and the solvation Aqueous [Fe(bpy)3]2+
Transient Solute structure (100 ps) Solvation structure (100 ps)
TRWAXS at 25.2 keV with ML mono (ID09, ESRF) AIMD by L. M. Lawson Daku L. M. Lawson Daku, PCCP, (2018)
D. Khakhulin et al. Phys. Chem. Chem. Phys., 21, 9277 (2019)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Further examples for femtosecond solution WAXS: bond formation and solvent coordination
van Driel, T., et al. Nat. Commun. 7, 13678 (2016)
[Ir2(dimen)4]2+ Q (Å-1)
[Au(CN)-2]3
K. Kim, et al. Nature 518, 385 (2015)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Further examples for femtosecond solution WAXS: vibrational wavepacket dynamics
K. Kunnus et al., Nat. Commun. 11, 634 (2020) K. Haldrup et al., Phys. Rev. Lett. 122, 063001 (2019)
Fe-carbenes PtPOP
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
High photon energy at European XFEL
8 x Si(531)
~ 77 mm
LaB6 diffraction collected with LPD @ 20 keV
Unique opportunities at high X-ray energies!
Nb K-edge ~19 keV
Large pixel detector (LPD)
0 ph
1 ph
2 ph
3 ph
ADU
Bin
Cou
nts
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
FXE instrument and experimental conditions for users
Parameter Unit 1st run 4th run
Photon energy (range)
keV ~ 9 (±0.3) keV) ~ 6 keV – 20 keV
Pulse number/train 1 – 30 1 – 300
Intra-train rep.-rate kHz 1128 1128, 564, 376, etc.
Pulse energy (at source)
µJ ~ 500 up to 4000
Bandwidth % 0.14* ca. 0.20 at 9.3 keV
Pointing stability µrad ~ 2 ~ 2
Focus size µm 10-30 ca. 8
Timing jitter (fwhm) fs 300 70
* calculated/simulated
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
FXE instrument: pump-probe results and user experiments
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Pump-probe X-ray emission spectroscopy on [Fe(bpy)3]- in aqueous solution
Kβ
Kα
Fe Kα difference spectra
Time delay / ps
IRF2 ≈ jitter2 + pulse width2 + GVM2
113 fs 70 fs 50 fs 100 fs
Thinner jets will enable better temporal resolution
Sample: 10 mM solution of [Fe(bpy)3]2+, 100 µm round jet Excitation: 400 nm, 50 fs, 2 µJ/pulse X-ray probe: 9.3 keV, 564 kHz, 100 pulses/train
“Ultrafast X-Ray Photochemistry at European XFEL: capabilities of FXE instrument” D. Khakhulin et al., Appl. Sci., 10(3), 995 (2020)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Femtosecond X-ray emission spectroscopy on [Fe(terpy)2]2+ in aqueous solution
Nax
Neq HS
W. Zhang et al., Nature, 509 (2014) 345
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Large Pixel Detector Scattering from 100 um water jet
Pump-probe X-ray scattering on [Fe(bpy)3]2+ aqueous solution
XFEL: 5 min collection
ESRF: 2 h collection
Sample: 10 mM solution of [Fe(bpy)3]2+, 100 µm round jet Excitation: 400 nm, 50 fs, 2 µJ/pulse X-ray probe: 12 keV, 564 kHz, 90 pulses/train, ~170 µJ/pulse to stay in high gain stage of LPD
Difference scattering curves
“Ultrafast X-Ray Photochemistry at European XFEL: capabilities of FXE instrument” D. Khakhulin et al., Appl. Sci., 10(3), 995 (2020)
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Fe Kα Co Kα
Co K-alpha
Fe K-alpha
Simultaneous detection of both Iron Kα and Cobalt Kα emission No uncertainty about t0 and normalization
PI: Matthias Bauer (University of Paderborn) Noble-metal free dyads with FeII photosensitzer
-0,4 -0,2 0,0 0,2 0,4 0,6 0,8 1,0 1,2
-0,030
-0,015
0,000
0,015
0,030
Nor
m. I
nteg
r. C
ount
s - f
it [a
.u.]
Probe delay [ps]
Kα1 middle derived wavepacket Damped sin fit
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
[S. Mariager, D. Khakhulin et al., NanoLett. (2010)]
Radial Breathing Tbr ~ R / vR
Axial Extension Text ~ L / vL
Bending Tben ~ L2/RvL
Tracking acoustic vibrations in semiconductor NWs by TR-GIXD
0 200 400 600 800
0.0
7.0x10-5
1.4x10-4
2.1x10-4
4 bunch mode (τx-ray≈ 130 ps) hybrid mode (τx-ray≈ 95 ps)
∆a/a
Delay [ps]
[D. Khakhulin et al. Acta Cryst. (2016). A72]
Diamond detector
High speed chopper
Storage ring
X-ray probe 1 kHz, 100 ps
Fast GaAs detector
Sample
dnw = 450 nm
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Jungfrau Detector
Sample position
Pump-probe grazing incidence XRD on semiconductor NWs
Tracking the transient lattice strain in NWs by monitoring Bragg peak position vs time delay
9.3 keV, τx-ray ≈ 50 fs rep. rate 10Hz
λ = 515 nm τlas = 0.8 ps rep.rate 10 Hz
Grazing incidence: α ≤ 2°
Jungfrau detector
Beams on sample Burn marks on sample
PI: V. Dubrovskii, ITMO, Russia
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Pump-probe GI diffraction with a SASE spectrum of the European XFEL
Single-shot spectrum (HIREX) [by N. Kujala (EuXFEL)]
InAs NW Bragg peak position variations shot-to-shot
Average spectrum over 1100 shots
Delay scan
Delay [ps]
Courtesy of R. Kurta (EuXFEL)
PI: V. Dubrovskii, ITMO, Russia
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
Summary Combined measurements of fs hard X-ray emission and solution scattering
are possible at FXE and result in high quality data with temporal resolution
down to 100 fs even without timing jitter correction
Performed FXE’s first fs X-ray emission spectroscopy and diffraction
experiments on solids both in transmission and grazing incidence geometry.
Development of specific instrumentation and advances sample environment is
ongoing
Upcoming commissioning campaigns are focused on developing advanced X-
ray absorption spectroscopy as well as 2D photon in/photon out
spectroscopies such as RXES (Johann spectrometer)
Check the status at www.xfel.eu/facility/instruments/fxe and subscribe to FXE newsletter
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
FXE group (EuXFEL) Christian Bressler Mykola Biednov Andreas Galler (now XO) Wojciech Gawelda Katharina Kubicek Frederico Lima Peter Zalden Angel Rodriguez-Fernandes Yifeng Jiang Martin Knoll Paul Frankenberger Timo Korsch Graduate students Christina Bömer Michael Diez Tae Kyu Choi Florian Otte
Acknowledgements EPFL Majed Chergui Camila Bacellar Oliviero Cannelli Dominik Kinschel Giulia Mancini Rebecca Ingle Uni Paderborm: Matthias Bauer Marina Huber ITMO Vladimir Dubrovskii Rodion Reznik George Cirlin
Hamburg (DESY/EuXFEL) Maria Naumova Aleksandr Kalinko Ruslan Kurta Naresh Kujala Wigner Budapest Zoltán Németh György Vankó
ESRF Michael Wulff Denis Leshchev
ELI-ALPS/DESY Sophie Canton Uni Geneva Latévi Max Lawson Daku
Uni Warsaw Jerzy Antonowicz Ryszard Sobierajski
Ultrafast photochemistry and photophysics at FXE, 07.05.2020 Dmitry Khakhulin, FXE group, European XFEL
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