brazilian synchrotron radiation and laser/x-rays experiments · sirius: project status -...
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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
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Outline
✓ History of X-rays
✓ Synchrotron Radiation
✓ LNLS & SIRIUS: Synchrotron Radiation in Brazil
✓ Examples: Ultrafast science
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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
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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
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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
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Sirius: the New Brazilian Synchrotron Radiation Source
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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)*
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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!
➟
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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
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Sirius: the beamlines 5 beamlines in 2018 13 beamlines in 2020
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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"
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SIRIUS: project status
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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.
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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
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Picture taken Oct. 14th 2014
Sirius: project status
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Picture taken Oct. 14th 2014
Sirius: project status
Sept. 2013
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Picture taken Oct. 14th 2014
Sirius: project status
Oct. 2014
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Picture taken Oct. 14th 2014
Sirius: project status
Jun. 2015
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Picture taken Oct. 14th 2014
Sirius: project status
Aug. 2016
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SIRIUS: project status
https://www.youtube.com/watch?v=l9S7Bu_j_n0
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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
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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.
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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)
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Pump-probe spectroscopy
beforeafter
Altdorf
Wilhelm Tell legend
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Electron filling mode at a modern synchrotron
http://www.esrf.eu/UsersAndScience/Experiments/MaterialsScience/ID09B/ExperimentsHutch/chopper/
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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
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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!
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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
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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’
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Femtosecond X-rays
G. Ingold, et al., AIP Conf. Proc., 879 (AIP, New York, 2006), p. 388, 2006.
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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.
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Ultrafast science
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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.
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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.
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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.
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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.
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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)
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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)
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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
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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
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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
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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.
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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
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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).
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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.
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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)
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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
➟
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Thank you