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

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

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

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

Towards Solvation Dynamics

-Distinguish IVR fromgguest-host interactions

-Example: NO/Rg matrixExample: NO/Rg matrix

Rydberg NO in rare gas matrices: bubble formation

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 ...

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

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

Now to something completely different….LS HS

10C. Consani et al.

Angew Chem (2009)

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

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)

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

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 !!

Spin sensitivity e

IP3p

IP

2p

1s

Courtesy: Pieter Glatzel (ESRF)

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

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)

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)

MHz Laser Installation at ESRF

Ready to Pump-Probe at MHz rep-rates!!Ready to Pump-Probe at MHz rep-rates!! 19

ID26 – X-ray Emission/Absorption Spectroscopy

201.4 MHz

ID26/ESRF (March 2011)( )

21

APS sector 7 (March 2011)APS, sector 7 (March 2011)

22

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

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)

XPP Commissioning (LCLS, Oct 2010) (Cammarata)

One single „File“ (10 min scan) at LCLSg ( )

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

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

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

Looking into the raw data…

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

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)

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 !!!

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)