Brazilian Synchrotron Radiation and Laser/X-rays experiments

Transcription

1 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

2 Outline History of X-rays Synchrotron Radiation LNLS & SIRIUS: Synchrotron Radiation in Brazil Examples: Ultrafast science

3 CNPEM - LNLS & SIRIUS LNLS: research and development using synchrotron radiation LNBio: research on biosciences LNNano: research on nano(materials) CTBE: research on ethanol production SIRIUS%

4 Synchrotron Radiation in Brazil Laboratório Nacional de Luz Síncrotron: LNLS - One out of the 4 labs (LNLS, LNNano, LNBio & CTBE) of the CNPEM - 18 beamlines operating

5 Synchrotron Radiation: LNLS 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

6 Sirius: the New Brazilian Synchrotron Radiation Source

7 Sirius: the New Brazilian Synchrotron Radiation Source 3$GeV$BOOSTER$ 3$GeV$STORAGE$RING$ 165$m$ 150$MeV$LINAC$ 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( 7*m*straight* sec9ons* 2*T*dipole*(PM)* 6*m*straight* sec9ons* Booster' Circumference' Cycling'frequency' ' 496.8''m' 3.5''nm.rad' 2''Hz' quadrupole* doublet* 0.58*T*dipoles* quadrupole* triplet*

8 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!

9 Sirius: brilliance Upgrade 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

10 Sirius: the beamlines 5 beamlines in beamlines in 2020

11 Sirius: the building 6"extra(long"beamlines" (150(100"m)" 3"GeV"booster"and"SR" in"the"same"tunnel" Engineering" service"area" 150"MeV"Linac" Experimental"hall" Tunnel"access"from" inside:"10"chicanes" Tunnel"access"from"top:" 20"openings"" (up"to"3x20"ton"cranes)" "

12 SIRIUS: project status

13 Sirius: project status Detailed Engineering Design Concluded - Definition of floor, facilities, etc. more complex than expected. - Technical areas ended up larger than initially expected (from ~ m 2 to ~ m 2 ). - 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.

14 Sirius: project status Revised Schedule (2014) Nov selection of construction company Nov start of machine installations mid 2018 start of SR commissioning Revised Budget (2014) Accelerators R$ 228 M 13 beamlines R$ 220 M Building R$ 668 M Human Resources R$ 88 M Contingencies R$ 96 M TOTAL R$ 1300 M

15 Sirius: project status Picture taken Oct. 14 th 2014

16 Sirius: project status Picture taken Oct. 14 th 2014 Sept. 2013

17 Sirius: project status Picture taken Oct Oct. 14 th 2014

18 Sirius: project status Picture taken Oct. 14 th 2014 Jun. 2015

19 Sirius: project status Picture taken Oct. 14 th 2014 Aug. 2016

20 SIRIUS: project status

21 Why do we need to study structure Structure - X-ray crystallography - electron microscopy - atomic force microscopy - electron diffraction - X-ray absorption spectroscopy - NMR Dynamics - Laser spectroscopy - NMR - Time-resolved diffraction & XAS - Time-resolved PES Graphene Manganite: atomic motion coupled by charge and orbital order Fullerene Photosystem II Nanotube Rotating hydrated Mb molecule Layer-selective spin dynamics in magnetic multilayers

22 Femtochemistry 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 sec.) Chemistry Novel Prize in 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. Energy excited state short-lived transition states back to ground state 1. Laser pulse starts the reaction t = 0 Δt 2. Laser pulse takes snapshots t Temporal evolution of the reaction

23 Some important time scales average age of marriage time of my PhD program age ~20-25 of universe years 4.3 years ~14 (6-8*10 billion 8 years sec) (1.3*10 8 sec) (4.5*10 17 sec) coffee break Hemoglobin transition R -> T camera shutter speed ~10 min (10-6 sec) (10-3 sec) (6*10 2 sec)

24 Pump-probe spectroscopy Altdorf before after Wilhelm Tell legend

25 Electron filling mode at a modern synchrotron

26 Selecting X-ray pulses: electronic gate Laser pump - x-ray probe MHz data acquisition Use all the camshaft x-rays camshaft 1.04 MHz camshaft multibunch Laser and x-ray are synchronized! x-ray focusing (KB mirrors) probe Laser system monochromator pump liquid flow Lima, F. A., Review of Scientific Instruments, vol. 82, (2011) DAQ

27 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!

28 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 Laser-slicing technique Wiggler Dispersive elements Undulator 1. Modulation 2. Separation 3. Radiation The FEMTO slicing source at the SLS - tunable from 4 to 14 kev ± 30 fs x-ray pulse duration - timing stability of < 30 fs RMS over days photons/second R. Schoenlein, et al., Science, 287: (2000) R. Schoenlein, et al., Appl. Phys. B, 71:1 10 (2000) P. Beaud, et al., Phys. Rev. Lett. 99, (2007)

29 Femtosecond X-rays: slicing scheme Calculation of the election distribution after the spatial dispersion Using slits one can separate the radiation emitted bye each portion of the sliced bunch 3 x a 8 x 4 x a 8 x -3 a 3 x x R. Schoenlein, et al., Science, 287: , R. Schoenlein, et al., Appl. Phys. B, 71:1 10, 2000.

30 Femtosecond X-rays G. Ingold, et al., AIP Conf. Proc., 879 (AIP, New York, 2006), p. 388, 2006.

31 X-ray Free-Electron Lasers Resonant 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. SASE - Self Amplified Spontaneous Emission Micro-bunching rad = (1 + K2 eff /2) K eff =0.934 rad B eff Long undulators are needed as the saturation of the micro-bunching effect is a function of the length.

32 Ultrafast science

33 Ultrafast protein diffraction: MbCO F. Schotte, et al., Watching a protein as it functions with 150-ps time-resolved x-ray crystallography. Science, 300: , 2003.

34 Ultrafast protein diffraction: MbCO F. Schotte, et al., Watching a protein as it functions with 150-ps time-resolved x-ray crystallography. Science, 300: , 2003.

35 Ultrafast protein diffraction: MbCO F. Schotte, et al., Watching a protein as it functions with 150-ps time-resolved x-ray crystallography. Science, 300: , 2003.

36 Ultrafast protein diffraction: MbCO F. Schotte, et al., Watching a protein as it functions with 150-ps time-resolved x-ray crystallography. Science, 300: , 2003.

37 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? 1 X. Ye et al. JACS. 124(20), 5914 (2002) 2 D. Nutt et al. J. Phys. Chem. B 109, (2005) 3 S. Kruglik et al. PNAS 107, (2010) time

38 MbNO - dynamics of ligand detachment A domed ligated (6-coordinated) configuration 1 with 30 ps lifetime was observed using ultrafast Raman spectroscopy. Multiple transient 50 ps. Analysis using MXAN - equivalent configuration are not distinguishable. Fast dynamics (ca. 200 ps) captured on the fly! Norm. Abs. [a.u.] Norm. Abs. [a.u.] MbNO transient MbNO deoxymb MbNO transient at 50 ps MXAN best fit Norm. Abs. [a.u.] Norm Abs(t) [a.u.] ~192 ps Relative x-ray x-ray energy [ev] [ev] Silatani, M., Lima, F. A., et al., PNAS 112 (42) pp (2015) Time delay [ps] Kruglik, S.G., et al., PNAS 107 (31) pp (2010) Lima, F. A., et al., (2011) PhD thesis, EPFL.

39 Ultrafast diffraction on Bismuth Ultrafast diffraction on bismuth crystal and coherent control K. Sokolowski-Tinten,et al., Nature, 422: , P. Beaud, et al., Physical Review Letters, 99(174801), 2007.

40 Ultrafast spin crossover: K-edge XAS Light-induced spin transition. Fe-N bond elongation upon spin transition t =50 ps t 2g h nm e g low-spin high-spin R Fe N =0.2 Å Gawelda, W., PhD thesis, EPFL (2006) Gawelda, W., et al., Physical Review Letters, 98, (2007). Gawelda, W., et al., J. Chem. Phys., 130, (2009).

41 Ultrafast spin crossover: L-edge XAS Non-equilibrium excited-state dynamics of a spin-crossover and their interplay with structural changes Zhang, W., et al., Nature, 509 pp (2014)

42 Ultrafast intramolecular electron transfer 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. Canton, S. E., et al., Nature Communications, 6 pp (2014)

43 Ultrafast bond formation Absorption (norm.) / a.u Transient EXAFS spectrum Δt = ns Absorption (norm.) / a.u. -2.0x10-3 Δ Pt - Pt = 0.31(5) Å Energy / kev Δ Pt - Ligand = 0.010(6) Å f = 7%, ΔE = 0 Photo-excitation in the first excited state induces a Pt-Pt bond formation. R.M. van der Veen, et al., Angew. Chem. Int. Ed. 48, 2711 (2009) R.M. van der Veen, et al., PCCP. 12(21) (2010) M. Christensen, et al., JACS. 131(2) (2009)

44 Ultrafast solvation dynamics Abs (norm.) / a.u.!abs (norm.) / 10-3 a.u. 50 ps after multi-photon excitation at 400 nm Increase in the solvent cage radius of 5-20% (a) (b) 4540 A 4560 B Energy / ev 4640 G(r) G(r) 3.5 (a) (a) (b) I-O iodide iodine QM/MM iodine CMD 5 R (Å) (b) 2 3 I-H 4 5 R (Å) Pham, V-T., et al., J. Am. Chem. Soc, 129, 1530 (2007). Pham, V-T., et al., J. Am. Chem. Soc, 133, (2011).

45 Protein Structural Dynamics: Scattering Ultrafast time-resolved Wide-angle X-ray Scattering Tertiary and quaternary conformational changes of human Hemoglobin triggered by laser-induced ligand photolysis. Cammarata, M., et al., Nature Methods 5 (10), pp (2008)

46 X-ray excited optical luminescence (XEOL) Photon-in/photon-out technique & site-selective Setup at TGM (3-330 ev) and XAFS2 ( kev) beamlines at LNLS - Excitation - Emission - Time-resolved studies using single-bunch mode (ns) (fluorescence and persistence) CYAM:Tb 3+ 3D map around the optical band gap in the vacuum ultraviolet/soft x-rays energy range. Bispo, et al. 2016, private communication Teixeira, V.C.., et al., Optical Express 36, pp (2014)

47 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

48 Thank you