time-resolved x-ray spectroscopies and scattering with one … · 2013-12-19 · time-resolved...
TRANSCRIPT
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Time-Resolved X-Ray Spectroscopies and Scattering Spectroscopies and Scattering
with One Trillion Photons
Christian BresslerChristian Bressler
XDL Workshop “tickle and probe”, Cornell University, June 21, 2011
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Dynamic Studies in Photochemistry
1. Intramolecular0 3
0,4
0,5
n / a
.u.
Ru(bpy)3 (aq)
Charge Transfer2835 2840 2845
0,0
0,1
0,2
0,3
Abs
orpt
ion
X-Ray Probe Energy / eVX Ray Probe Energy / eV
2. TowardsSolvation Dynamics 0,5
1,0
I-
I0
Abs
orpt
ion
/ a.u
.
F (b ) ( )
5180 5200 5220
0,0
X-Ray Probe Energy (eV)Nascent I0 (aq)
3. Light-InducedSpin Crossover
Fe(bpy)3 (aq)
Spin Crossover
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What are the fundamental timescales?Chemistry and Biochemistry
Molecular
PhotosynthesisVision
S i M l l r R t ti n
Protein Folding
MolecularVibrations
P ti lStrings, Cosmology
Molecular Rotations
El d i
Particle Collisions
Electron dynamics
harpo10-27
yacto10-24
milli10-3
micro10-6
nano10-9
pico10-12
femto10-15
atto10-18
zepto10-21
Time /seconds
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Now for the low-lying fruit (K edges)
1021=
10
1018
r S/N
RIXS, X-Ray Raman
1015
ons
for
Valence XESTransm
109
1012
Pho
to K XES
Fluorescence XAFS
ansmission XAFS
106
109
cide
nt XAFS
0,1 1 10 100 1000
10
Inc
,Aqueous Sample Concentation / mM
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Towards Solvation Dynamics
-Distinguish IVR fromgguest-host interactions
-Example: NO/Rg matrixExample: NO/Rg matrix
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Rydberg NO in rare gas matrices: bubble formation
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Ultrafast Processes in the C nd n d Ph ( f n kind)
Speed of Sound: >10 Å/ps
Condensed Phase (of any kind)Speed of Sound: >10 Å/ps
100 1000 S l t M l l i l d…ca 100-1000 Solvent Molecules involved
X-Ray Absorption Spectroscopy X Ray Absorption Spectroscopy Singles Out Reaction Center ...
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Electron Detachment Reactions (via XAFS)
1,0
n / a
.u.
2s→5p
0,0
0,5 I-
I0
Abs
orpt
ion
Pham et al., JACS (2007)
5180 5200 5220
X-Ray Probe Energy (eV)
I. Tavernelli (EPFL)Nascent I atoms in solution
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EXAFS and XANES of nascent iodine radicals
static300 fs50 ps50 ps
50 ps
300 fs50 ps
50 psV.-T. Pham et al. Chem. Phys. (2010)
V.-T. Pham, PhD thesis (2010)
I0I-
V.-T. Pham et al. Submitted (2011)
I0
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Now to something completely different….LS HS
10C. Consani et al.
Angew Chem (2009)
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Towards Transient Structures via TR-XAFS
1
a.u.
01
LSA /
a
HS 50 ps
03
0
1
7100 7150
A x
1
∆RFe-N= 0.2 ±0.008 Å2 4 6 8 10
Photoelectron Wavevector k / Å-1
7100 7150
X-Ray Probe Energy / eV M. Benfatto (INFN Rome)
B0
1 t < 0
(k
) x k
2
B665 ps
1
-1
t = 50 ps
k2
Exp. (Ground State) Fit
70 ps0
(
k) x
k
Exp. (Transient) Fit
11 W. Gawelda et al. Phys. Rev. Lett. (2007)
W. Gawelda et al. J. Chem. Phys. (2009)
0 2 4 6 8 10-1
Photoelectron Wavevector k / Å-1
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ps and fs XANES (Synchrotron)
u.1
LSA /
a.u
HS
0
A
50 ps
3
1
x 10
3 300 fs
0
A
7100 7150
X Ray Probe Energy / eV
X-Ray Probe Energy / eVC. Bressler et al., Science (2009)
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Identifying intermediate states...
∆RF N =0.2 Å
y g
∆RFe-N 0.2 Å
-500 0 500 1000Time Delay / fs
250 fs (instrument response):
140(30) fs hard x-ray pulse115(10) fs laser pulse
10-12 photons/pulse (2 kHz, 2 eV BW)<100(30) fs time zero drifts
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Combined optical and x-ray results
1MLCTb)??
120 fs
MLCT
y
3MLCT20 fs
)
<130 fs
Ene
rgy
E
5T (HS)2
665 ps
R (Fe-N)
1A (LS)1
Need now a Spin-Sensitive Tool !! Need now a Spin Sensitive Tool !!
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Spin sensitivity e
IP3p
IP
2p
1s
Courtesy: Pieter Glatzel (ESRF)
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1s XES of a spin transition molecule
1s2p 1s3p 1sVBexchange (J)
3dn p
1s
FeII— 3d6
S 0 2S = 0 2
T,p
hG. Vankó et al., J. Phys. Chem. B 110 (2006) 11647
h
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Towards ultrafast X-ray Emission Spectroscopy
103 – 106 ph/pulse (100 ps) 10 12 ph/pulse (200 fs)10-12 ph/pulse (200 fs)10-3 ph/pulse (100 ps XES)
X S
a) b)D1D2
T = 960 nsX S
c)L c)D3
0 5
Ge(440)Laser 0.5 ms
G. Vankó et al., Angew. Chem. Int. Ed. (2010)
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Direct spin probing: first TR-XES (ps)p p g (p )
Femtosecond Time Resolution Femtosecond Time Resolution Ideally suited for single wavelength
XFEL experiments MH titi t !!!! MHz repetition rates !!!!
G. Vanko et al., Angew. Chem. Int. Ed., (2010)
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MHz Laser Installation at ESRF
Ready to Pump-Probe at MHz rep-rates!!Ready to Pump-Probe at MHz rep-rates!! 19
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ID26 – X-ray Emission/Absorption Spectroscopy
201.4 MHz
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ID26/ESRF (March 2011)( )
21
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APS sector 7 (March 2011)APS, sector 7 (March 2011)
22
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Picosecond K alpha XES at APS
1 kH t di t 1 kHz pp studies at SLS
(Angew Chem 2010)(Angew. Chem. 2010)
0 13 MHz at APS0.13 MHz at APS
23
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back to the future:back to the future:
• Entering the femtosecond time scale (again)Linac coherent light source (LCLS)g ( )
• Credits: D. Fritz, M. Cammarata (SLAC)
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XPP Commissioning (LCLS, Oct 2010) (Cammarata)
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One single „File“ (10 min scan) at LCLSg ( )
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Oct 2010: XPP commissioningg
SLS (t = 50 ps)SLS (t 300 f )
SLS (t = 50 ps)SLS (t 300 f )
0,1
S /
a.u.
SLS (t = 300 fs) XPP (t = 250 fs)
0,1
SLS (t = 300 fs) XPP (t 300 fs)
XA
NE
S
0,0
ansi
ent
0,0
Tra
7100 7110 7120 7130 7140 7150 7160
X-Ray Probe Energy / eV7100 7110 7120 7130 7140 7150 7160
X-Ray Probe Energy / eVy gyy gy
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Real-Time Traces
n Science 2009
n Science 20090,003
sorp
tion Science 2009
Fit curve 2009 XPP 2010
0,003
sorp
tion Science 2009
Fit curve 2009 XPP 2010
0,002
sien
t Ab 0,002
sien
t Ab
0,001
ay T
rans 0,001
ay T
rans
0,000
X-R
a
0,000
X-R
a
-500 0 500 1000 1500-0,001
Laser-X-Ray Time Delay / fs-500 0 500 1000 1500
-0,001
Laser-X-Ray Time Delay / fsLaser X Ray Time Delay / fsLaser X Ray Time Delay / fs
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Transient Spectra around Time Zero0,06
0,036
S
0,04
XAN
ES0,034
sien
t XA
NE
S
0,02
X
-500 0 500 1000
0,032Tran
s
0,0025
NE
S
0,00Laser X-Ray Time Delay / fs
1,0
1GS
0 0000ansi
ent X
AN
0,8
0,9
5 S1,3MLCTop
ulat
ion
0,0000Tr
a
0 0
0,1Spin Flip?
5HS, MLCTPo
7110 7120 7130 7140
X-Ray Probe Energy / eV
-500 0 500 10000,0
Time / fs
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Looking into the raw data…
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Summary of combined optical/XAS studies??
120 fseg
t
??
t2g
a)
1T1
1T21,3MLCT
y
)
1,3T…:<60 fs
15E
Ener
gy
3T1
3T2
1A1
R (Fe-N)
5T2
Need to include XES (spin) and even XRD (solvent)…experiments at APS/ESRF to prepare for LCLS
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Next Step: Exploit Complementary Structural Tools(LCLS project 2011): Towards understanding chemical reactivity
XES: occupied DOS (spin)e- XES: occupied DOS (spin)
XAS: empty DOS (orbitals)
XRD: geometric structuresXRD: geometric structures
Collaboration:
M. Nielsen (Copenhagen)V S d t ö (L d)
1) Ru(II) Ru(III) (XAS XES optical)
V. Sundström (Lund)G. Vanko (Budapest)P. Glatzel (ESRF)
A M nt (P t 3)1) Ru(II) Ru(III) (XAS, XES, optical)
2) IVR + e-transport (XRD, optical)
3) Co(III) Co(II) (XAS XES optical)
A. Meents (Petra3)R. Abela (SwissFEL)
3) Co(III) Co(II) (XAS, XES, optical)
4) Co(II) LSHS (XAS, XES)
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Conclusions
Towards Solvation Dynamics 0,5
1,0
I-
I0
Abso
rptio
n / a
.u.
y5180 5200 5220
0,0 I
X-Ray Probe Energy (eV)Nascent I0 (aq)
- We can follow the sequence of events from 300 fs onwardsqEven the (few) ps time scale we do not fully understand Theoretical input important
W d t k h thi l b t 0 300 f- We need to know how things evolve between 0-300 fs New experiments are planned (theory required)
Light-InducedSpin Crossover
Fe(bpy)3 (aq)
Spin Crossover
- We do not understand this correlated SCO behavior!…but we are already looking into the elementary steps !!!
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AcknowledgmentsAcknowledgments 34
Argonne National Lab (APS)- Steven Southworth
University of Copenhagen- Martin Meedom Nielsen
- Anne-Marie March (MHz laser) - Gilles Doumy- Elliot Kanter
- Kristoffer HaldrupLund University
Villy Sundström Elliot Kanter- Dipanwita Ray- Robert Dunford- Linda Young
- Villy Sundström- Sophie Canton- Jens Uhlig
G i S l - Linda Young- Grigory SmolentsevKFKI Budapest- György VankóSwissFEL
R f l Ab l
ESRFPieter Glatzel
y gy- Rafael Abela
European XFEL Facility- Wojciech Gawelda- Pieter Glatzel
- Erik GalloWojciech Gawelda
- Andreas Galler
LCLS (SLAC) K. Gaffney, L. X. Chen, H. Ihee( )- David Fritz, Marco Cammarata
y, ,(XPP Oct 2010)