Brazilian Synchrotron Radiation and Laser/X-rays experiments

Frederico Alves Lima Centro Nacional de Pesquisa em Energia e Materiais - CNPEM Laboratório Nacional de Luz Síncrotron - LNLS

International School on Laser-Beam Interactions UFRN - Natal, Brazil September 2016

Outline

✓ History of X-rays

✓ Synchrotron Radiation

✓ LNLS & SIRIUS: Synchrotron Radiation in Brazil

✓ Examples: Ultrafast science

CNPEM - LNLS & SIRIUS

SIRIUS%

LNLS: research and development using synchrotron radiation

LNBio: research on biosciences

LNNano: research on nano(materials)

CTBE: research on ethanol production

Synchrotron Radiation in Brazil

http://lnls.cnpem.br/

Laboratório Nacional de Luz Síncrotron: LNLS

- One out of the 4 labs (LNLS, LNNano, LNBio & CTBE) of the CNPEM

- 18 beamlines operating

Synchrotron Radiation: LNLS

http://lnls.cnpem.br/beamlines/

Diffraction XRD1, XRD2, XPD, XDS*

Hard X-rays Spectroscopy XAFS1, XAFS2, DXAS, XRF XDS*

Soft X-rays Spectroscopy SXS, PGM, TGM, SGM

X-ray Scattering SAXS1, SAXS2

Macromolecular Crystallography MX1, MX2

X-ray Imaging & Infrared tomography and microscopy

Sirius: the New Brazilian Synchrotron Radiation Source

Sirius: the New Brazilian Synchrotron Radiation Source

150$MeV$LINAC$

3$GeV$BOOSTER$

3$GeV$STORAGE$RING$

165$m$

Booster' ''

Circumference' 496.8''m'

Emi5ance'@'3'GeV' 3.5''nm.rad'

Cycling'frequency' 2''Hz'

Storage(Ring(

Beam(energy( 3.0((GeV(

Circumference( 518.4((m(

La=ce( 20(x(5BA(

Straight(secCons( 10(x(7m,((10(x(6m(

Current,(top(up( 350((mA(

Betatron(tunes((H(/(V)( 48.25(/(13.15(

Hor.(EmiMance(( 190(O(270((pm.rad(

Vert.(emiMance((k=1%)( 2.7((pm.rad(

Number(of(bunches( 864(

Bunch(length( 10((ps(

Energy(spread( 0.083(%(

RF(frequency( 500((MHz(

quadrupole*doublet* 0.58*T*dipoles*

quadrupole*triplet*

7*m*straight*sec9ons*

6*m*straight*sec9ons*

2*T*dipole*(PM)*

Sirius: brilliance

New magnetic lattice (5-bend achromat) results in a machine with a very small emittance

Several orders of magnitude increase in beam brilliance!

➟

Sirius: brillianceUpgrade in the magnetic lattice resulted in a better machine of the electron and photon beam emittance

Electron and photon beam convolution: 25% increase in brightness at 1 keV and 13% at 10 keV

Sirius: the beamlines 5 beamlines in 2018 13 beamlines in 2020

Sirius: the building

6"extra(long"beamlines"(150(100"m)"

Tunnel"access"from"top:"20"openings""(up"to"3x20"ton"cranes)""

150"MeV"Linac"

3"GeV"booster"and"SR"in"the"same"tunnel"

Engineering"service"area"

Experimental"hall" Tunnel"access"from"inside:"10"chicanes"

SIRIUS: project status

Sirius: project status

- Definition of floor, facilities, etc. more complex than expected.

- Technical areas ended up larger than initially expected(from ~44.000 m2 to ~68.000 m2).

Detailed Engineering Design Concluded

- Some engineering items ( fl o o r, b u i l d i n g , a i r conditioning, etc.) are difficult to project. There are many uncontrolled variables resulting in the lack of good predictive models.

Revised Budget (2014)Accelerators R$ 228 M13 beamlines R$ 220 M

Building R$ 668 MHuman Resources R$ 88 M

Contingencies R$ 96 MTOTAL R$ 1300 M

Revised Schedule (2014) Nov. 2014selection of construction company Nov. 2017start of machine installations mid 2018 start of SR commissioning

Sirius: project status

Picture taken Oct. 14th 2014

Sirius: project status

Picture taken Oct. 14th 2014

Sirius: project status

Sept. 2013

Picture taken Oct. 14th 2014

Sirius: project status

Oct. 2014

Picture taken Oct. 14th 2014

Sirius: project status

Jun. 2015

Picture taken Oct. 14th 2014

Sirius: project status

Aug. 2016

SIRIUS: project status

https://www.youtube.com/watch?v=l9S7Bu_j_n0

Why do we need to study “structure”

Structure Dynamics- X-ray crystallography - electron microscopy - atomic force microscopy - electron diffraction - X-ray absorption spectroscopy - NMR

- Laser spectroscopy - NMR - Time-resolved diffraction & XAS - Time-resolved PES

Photosystem II Rotating hydrated Mb molecule

Graphene

Nanotube

Fullerene

Manganite: atomic motion coupled by charge and orbital order

Layer-selective spin dynamics in magnetic multilayers

Femtochemistry

Energy

t = 0 t ⇾ ∞

excited state

1. Laser pulse starts the reaction

Δt

short-lived transition states

back to ground state

Temporal evolution of the reaction

2. Laser pulse takes snapshots

The advent of pulsed lasers with ultrafast pulse duration (fs) motivated the creation of a new area of science. Femtochemistry: the study of chemical reactions and phenomena in an ultrafast temporal scale (femtosecond = down to 10-15 sec.)

Chemistry Novel Prize in 1999 - Ahmed H. Zewail "for his studies of the transition states of chemical reactions using femtosecond spectroscopy”

Pump-and-probe spectroscopy two (or more) light pulses with variable temporal separation are used to investigate whichever processes occurring during a chemical reaction, electronic or spin transition, quasi-particle excitation, impulsive atomic movement, etc.

Some important time scales

age of universe ~14 billion years

(4.5*1017 sec)

average age of marriage ~20-25 years (6-8*108 sec)

time of my PhD program 4.3 years

(1.3*108 sec)

coffee break ~10 min

(6*102 sec)camera shutter speed

(10-3 sec)

Hemoglobin transition R -> T (10-6 sec)

Pump-probe spectroscopy

beforeafter

Altdorf

Wilhelm Tell legend

Electron filling mode at a modern synchrotron

http://www.esrf.eu/UsersAndScience/Experiments/MaterialsScience/ID09B/ExperimentsHutch/chopper/

Selecting X-ray pulses: electronic gate

DAQ

liquid flow

multibunch

1.04 MHz

pump

probe

monochromator

x-ray focusing (KB mirrors)

Laser system

Laser and x-ray are synchronized!

camshaftcamshaft

Lima, F. A., Review of Scientific Instruments, vol. 82, 063111 (2011)

✓ Laser pump - x-ray probe

✓ MHz data acquisition

✓ Use all the ‘camshaft’ x-rays

Selecting X-ray pulses: X-ray chopper

Titanium triangular rotor with a channel on each side is installed in the beamline (in vacuum) very close to the sample to benefit from the small beam size.Can select individual pulses depending on the storage ring filling pattern.

Quite a complicated operation!

Femtosecond X-rays: slicing scheme- An ultrashort (fs) laser pulse co-propagate with an electron bunch causing a modulation on its energy - Electrons with different energy are further separate in space via dispersive elements on the synchrotron ring

R. Schoenlein, et al., Science, 287:2237–2240 (2000) R. Schoenlein, et al., Appl. Phys. B, 71:1–10 (2000) P. Beaud, et al., Phys. Rev. Lett. 99, 174801 (2007)

The FEMTO slicing source at the SLS - tunable from 4 to 14 keV - 140 ± 30 fs x-ray pulse duration - timing stability of < 30 fs RMS over days - 105 photons/second

WigglerDispersive elements Undulator

1. Modulation 2. Separation 3. Radiation

Laser-slicing technique

Femtosecond X-rays: slicing scheme

R. Schoenlein, et al., Science, 287:2237–2240, 2000. R. Schoenlein, et al., Appl. Phys. B, 71:1–10, 2000.

-3 a 3�x �x

3 a 8�x �x 4 a 8�x �x

Calculation of the election distribution after the spatial dispersion

Using slits one can separate the radiation emitted bye each portion of the ‘sliced bunch’

Femtosecond X-rays

G. Ingold, et al., AIP Conf. Proc., 879 (AIP, New York, 2006), p. 388, 2006.

X-ray Free-Electron LasersResonant condition: The slippage between the electromagnetic wave and a given electron, while the electron advances by one undulator period must be equal to the field wavelength.

Micro-bunching⇥rad =

⇥0

2�2(1 + K2

eff/2)

Keff = 0.934�radBeff

➟

SASE - Self Amplified Spontaneous Emission

Long undulators are needed as the saturation of the micro-bunching effect is a function of the length.

Ultrafast science

Ultrafast protein diffraction: MbCO

F. Schotte, et al., Watching a protein as it functions with 150-ps time-resolved x-ray crystallography. Science, 300:1944–1947, 2003.

Ultrafast protein diffraction: MbCO

F. Schotte, et al., Watching a protein as it functions with 150-ps time-resolved x-ray crystallography. Science, 300:1944–1947, 2003.

Ultrafast protein diffraction: MbCO

F. Schotte, et al., Watching a protein as it functions with 150-ps time-resolved x-ray crystallography. Science, 300:1944–1947, 2003.

Ultrafast protein diffraction: MbCO

F. Schotte, et al., Watching a protein as it functions with 150-ps time-resolved x-ray crystallography. Science, 300:1944–1947, 2003.

Dynamics of ligand detachment in Myoglobin

✓ Irradiation with light ➱ mimic biological function

✓ How fast is the ligand recombination?

✓ Is it geminate or non-geminate?

✓ Excitation yield of photo-detachment 1

- 100% for MbCO

- 50% for MbNO

✓ What’s the geometry of the transient structure? 2,3

time

?1 X. Ye et al. JACS. 124(20), 5914 (2002) 2 D. Nutt et al. J. Phys. Chem. B 109, 21118 (2005) 3 S. Kruglik et al. PNAS 107, 13678 (2010)

0.020

0.015

0.010

0.005

0.000

-0.005

Norm

. ∆Ab

s. [

a.u.

]

806040200

Relative x-ray energy [eV]

MbNO transient at 50 ps MXAN best fit

MbNO - dynamics of ligand detachment

0.020

0.015

0.010

0.005

0.000

-0.005

Norm

. ∆Ab

s. [a

.u.]

806040200

Relative x-ray energy [eV]

1.2

1.0

0.8

0.6

0.4

0.2

0.0

Norm. Abs. [a.u.]

MbNO transient MbNO deoxyMb

1 Kruglik, S.G., et al., PNAS 107 (31) pp. 13678 (2010) Lima, F. A., et al., (2011) PhD thesis, EPFL.

A domed ligated (6-coordinated) configuration1 with 30 ps lifetime was observed using ultrafast Raman spectroscopy.

Multiple transient structures @ 50 ps.

Analysis using MXAN - equivalent configuration are not distinguishable.

Fast dynamics (ca. 200 ps) captured on the fly!

1.0

0.8

0.6

0.4

0.2

0.0

-0.2

Norm

∆Ab

s(t)

[a.

u.]

120010008006004002000

Time delay [ps]

~192 ps

Silatani, M., Lima, F. A., et al., PNAS 112 (42) pp. 12922 (2015)

Ultrafast diffraction on Bismuth

K. Sokolowski-Tinten,et al., Nature, 422:287–289, 2003. P. Beaud, et al., Physical Review Letters, 99(174801), 2007.

Ultrafast diffraction on bismuth crystal and coherent control

Ultrafast spin crossover: K-edge XAS

�RFe�N = 0.2 A

t =50 ps�

Gawelda, W., PhD thesis, EPFL (2006) Gawelda, W., et al., Physical Review Letters, 98, 057401 (2007). Gawelda, W., et al., J. Chem. Phys., 130, 124520 (2009).

h�

350� 550nm

low-spin high-spin

egt2g

✓ Light-induced spin transition.

✓ Fe-N bond elongation upon spin transition

Ultrafast spin crossover: L-edge XAS

Zhang, W., et al., Nature, 509 pp. 345-348 (2014)

Non-equilibrium excited-state dynamics of a spin-crossover and their interplay with structural changes

Ultrafast intramolecular electron transfer

Canton, S. E., et al., Nature Communications, 6 pp. 6359 (2014)

Non-equilibrium ultrafast dynamics of a bimetallic donor–acceptor complex: light-harvesting Ru and optically dark Co

First direct observation of intramolecular electron transfer process over large interatomic distances.

Ultrafast bond formation

1.10

1.05

1.00

0.95

0.90

Ab

so

rptio

n (

no

rm.)

/ a

.u.

11.9011.8511.8011.7511.7011.65

Energy / keV

-2.0x10-3

-1.0

0.0

1.0

2.0

∆ A

bso

rptio

n (n

orm

.) / a.u

.

R.M. van der Veen, et al., Angew. Chem. Int. Ed. 48, 2711 (2009) R.M. van der Veen, et al., PCCP. 12(21) 5551-5561 (2010) M. Christensen, et al., JACS. 131(2) 502-508 (2009)

Transient EXAFS spectrum Δt = 0 - 150 ns

Photo-excitation in the first excited

state induces a Pt-Pt bond formation.

Δ Pt - Pt = 0.31(5) Å

f = 7%, ΔE = 0

Δ Pt - Ligand = 0.010(6) Å

Ultrafast solvation dynamics

50 ps after multi-photon excitation at 400 nm Increase in the solvent cage radius of 5-20%

1.2

0.8

0.4

0.0

Abs (

norm

.) / a

.u.

464046204600458045604540

Energy / eV

-15

0

15

!A

bs (

norm

.) / 10

-3 a

.u.

A

B

(a)

(b)

0 0.5

1 1.5

2 2.5

3 3.5

G(r)

(a)

0 0.5

1 1.5

2 2.5

87654321

G(r)

R (Å)

(b)

0 0.5

1 1.5

2 2.5

3 3.5

G(r)

(a)

0 0.5

1 1.5

2 2.5

87654321

G(r)

R (Å)

(b)

0 0.5

1 1.5

2 2.5

3 3.5

G(r)

(a)

0 0.5

1 1.5

2 2.5

87654321

G(r)

R (Å)

(b)I-O I-Hiodideiodine QM/MMiodine CMD

Pham, V-T., et al., J. Am. Chem. Soc, 129, 1530 (2007). Pham, V-T., et al., J. Am. Chem. Soc, 133, 12740 (2011).

Protein Structural Dynamics: Scattering

Cammarata, M., et al., Nature Methods 5 (10), pp. 881-886 (2008)

Ultrafast time-resolved Wide-angle X-ray Scattering

Tertiary and quaternary conformational changes of human Hemoglobin triggered by laser-induced ligand photolysis.

CYAM:Tb3+ 3D map around the optical band gap in thevacuum ultraviolet/soft x-rays energy range. Bispo, et al.2016, private communication

0 200 400 600 800 1000

107

108

109

1010

Ca2SnO4:Sm3+ (0.5 mol-%)Persistent luminescence (charge and decay)lem: 570 nm

Time / s

Inte

nsity

/ U

nid.

Arb

.

4.4 eV

5.2 eV

8.0 eV

0 100 200 300 400 500 60010-6

10-5

10-4

10-3

10-2 Sodium salicylateFluorescence decay - Single bunch mode

In

tens

ity /

Uni

d. A

rb.

Time / ns

Persistent time decay of Ca2SnO4: Sm3+ (left). Pedroso,et al., private communication, 2016 (left).Fluorescence time decay of sodium salicylate,measured in single bunch mode (right).

X-ray excited optical luminescence (XEOL)

• LNLS setup at the TGM beamline (vacuumultravioletand soft x-rays)– Excitation– Emission– Time-resolved studies: fluorescence (single bunch mode) and

persistence.

X-ray excited optical luminescence (XEOL)

View of the experimental setup for optical measurements at the TGM beamline

Photon-in/photon-out technique & site-selective

Setup at TGM (3-330 eV) and XAFS2 (3.5-17 keV) beamlines at LNLS - Excitation - Emission - Time-resolved studies using single-bunch mode (ns)

(fluorescence and persistence)

Teixeira, V.C.., et al., Optical Express 36, pp. 1580-1590 (2014)

Summary

✓ CNPEM is a multi-disciplinary research center with cutting edge equipment and staff

✓ Structure & dynamics are important to determine how materials function

✓ X-rays are suitable to study atomic scale

✓ Synchrotron light indispensable scientific & technologic tool

✓ Many different possibilities of applications of laser/photon interaction

➟

Thank you