workshop: inelastic x-ray scattering for nsls ii march 15 ...€¦ · ⇒indication of ring like...
TRANSCRIPT
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Recent Advances in Hard X-ray Inelastic Scattering with Medium Resolution
(A Story about Water)
Workshop: Inelastic X-ray Scattering for NSLS II March 15, 2004, Upton, NY
• motivation• x-ray Raman spectroscopy (XRS)• x-ray emission spectroscopy (XES)• selective x-ray absorption (S-XAS)• resonant inelastic x-ray scattering (RIXS)
Uwe Bergmann
SSRL, Stanford Linear Accelerator Center
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Anders Nilsson SSRL/Stockholm
Philippe Wernet BESSY
Lars Pettersson Stockholm
Jean-Louis Hazemann Grenoble
Pieter Glatzel UtrechtFrank de Groot
Steve Cramer LBNL/Davis
Vittal Yachandra Calvin Lab, LBNLJunko Yano
Beamline Staff SSRL 10-2, NSLS X-25, APS 18ID (BioCAT)
Collaborators
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Photon-in Photon-out X-ray Spectroscopy
x-ray beamfrom synchrotron
technique experimental procedure
x-ray Raman scattering (non resonant) scan of monochromator, analyzer fixedselective x-ray absorption
x-ray emission (non resonant) scan of analyzer, monochromator fixed
resonant inelastic x-ray scattering scan of both
monochromator
sampledetector
tunable analyzer
∆E ~ 1 eV
∆E ~ 1 eV
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hydrogen bonding
propertiesstructure
water“essential for life”
“organisms consist mostly of water”“most abundant substance on earth”
“only naturally occurring inorganic liquid”“third most common molecule in the universe”
…
The Local Structure of Water
criticalpoint
experimental techniques:- neutron and x-ray diffraction- infrared/fs spectroscopy- collective excitations (dynamics)
- XAS → local structure
soft
x-ray
s
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Photosynthetic Oxygen Evolution
CO2 + H2O → (CH2O)n + O2ћω
photosynthesis
this process generates carbohydrates and the world supply of oxygen
4 ћω
photosystem II cytochrome oxidase
how? life cycle
oxygen evolution
2 H2O → O2 + 4 H+ + 4 e-
the oxygen is derived from water
aerobic metabolismATP + CO2 + H2O ← (CH2O)n + O2
we consume oxygen to “burn” the energy of carbohydrates to produce ATP, the biological energy currency
- OEC is a 4 Mn cluster- four states S0 – S3- EPR, K-edge, EXAFS,
Kβ, crystallography- L-edge not possible
catalyticcenter
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Why water?
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Photon-in Photon-out X-ray Spectroscopy
technique experimental procedure
x-ray Raman scattering (non resonant) scan of scan of monochromatormonochromator, analyzer fixed, analyzer fixed
selective x-ray absorption
x-ray emission (non resonant) scan of analyzer, monochromator fixed
resonant inelastic x-ray scattering scan of both
monochromator
sampledetector
tunable analyzer
∆E ~ 1 eV
∆E ~ 1 eV
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Principle of X-ray Raman Spectroscopy
E0
∆E = E0 - E’
E’
sample
e-
photonphoton
6400 6500 6600 6700 6800 6900 7000 7100
elastic peak
E0 [eV]
Comptonpeak
Raman scattering
∆EIn
tens
ity
[l og
sca l
e ]
scattering probability: w ~ cos2θ sin2(θ/2) |<i|r|f>|2
for qr << 1, and |ki| ≅ |kf|
graphite
θ
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why XRS?
sample specific:- true bulk probe- no vacuum requirements- in situ experiments - high temperature/pressure
technique specific:- no saturation effects- non dipole transitions at large q- pump probe experiments (LCLS)
samples
in general:- any sample with sufficient
scattering strength
in particular:- systems not suited for studies
with conventional techniques- concentrated low Z systems- liquids- reactive specimens
Motivation
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Local Structure of Water
water (RT)
surface ice
ice90o CRT
data calculations
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• identification of large percentage of molecules with one
‘broken’ donor bond (SD)
⇒ indication of ring like configurations
• weak temperature dependence
hydrogen bonds per moleculeTemperature 25oC 90oC MD ~3.5 ~ 3.3 experiment ~2.1 ~ 2
classical MD uses pair potentials ⇒ possibly incomplete description of hydrogen bondsneeded: ab initio MD simulations with > 500 molecules
What the data suggest
Wernet et al, Science accepted
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Photon-in Photon-out X-ray Spectroscopy
technique experimental procedure
x-ray Raman scattering (non resonant) scan of scan of monochromatormonochromator, analyzer fixed, analyzer fixed
selective x-ray absorption
x-ray emission (non resonant) scan of analyzer, monochromator fixed
resonant inelastic x-ray scattering scan of both
monochromator
sampledetector
tunable analyzer
∆E ~ 1 eV
∆E ~ 1 eV
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why XES?
- direct probe of unpaired spins in 3d transition metals⇒ oxidation state, spin state
- sensitivity to ligand type and distance- ‘orientation’ of disordered sample
future: pump probe, single shot experiments (LCLS)
samples (5-12 keV)
- any sample (very dilute sample possible) - 3d transition metals (K-emission)- rare earths (L-emission)
Motivation
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Mn(II)OMn(IV)O2
KMn(VII)O4
Relative Energy [eV] 350
Inte
nsit
y [a
.u.]
Kα1
Kβ''
Kβ'
Kβ2,5
Kβ1,3
Kα2
10-5
10-4
10-3
10-2
1.5 1.7 1.9 2.1 2.3
Rela
tive
Int
egra
ted
Inte
nsit
y
Mn-O Distance [A]o
-25 -20 -15 -10 -5 0 5
K2MnF
6Mn salen NitridoKMnO
4
Energy Shift [eV]
Nor
mal
ized
Int
ensi
ty [a
.u.]
FO N
chemical sensitivity of K fluorescence
X-ray Emission Spectroscopy
valencelevels
3p
2p
1s
Kα1.2
Kβ1,3, Kβ’
Kβ2,5, Kβ’’
level diagram
Bergmann et al, Chem Phys Lett 302, 1999
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mono-µ-oxomanganese di-µ-oxo
manganese
di-µ-oxo (IV-IV)-(III-IV)
XANES difference spectra
Kβ XES difference spectra
XANES spectra
(III-III)(III-IV)(IV-IV)
(III-IV)(IV-IV)
mono-µ-oxo(III-IV)-(III-III)
mono-µ-oxo(IV-IV)-(III-IV)
Visser et al, JACS 123 7031, 2001
Comparison: XANES versus Kβ1,3 XES
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Kβ1,3 XES on Photosystem IIdifference spectra
Messinger et al, JACS 123, 7804, 2001
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Photon-in Photon-out X-ray Spectroscopy
technique experimental procedure
x-ray Raman scattering (non resonant)
selective x-ray absorption scan of scan of monochromatormonochromator, analyzer fixed, analyzer fixed
x-ray emission (non resonant) scan of analyzer, monochromator fixed
resonant inelastic x-ray scattering scan of both
monochromator
sampledetector
tunable analyzer
∆E ~ 1 eV
∆E ~ 1 eV
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Motivation
why selective selective EXAFS?
- chemical in addition to elemental specificity- extended k-range ⇒ higher resolution
samples
- any sample- e.g. 3d metals, rare earths
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Extending the Resolution of EXAFS from 0.15 to 0.10 Å
S1 : 2 to 3 Mn-Mn at 2.72 - 2.84 Å
S2 : 2 to 3 Mn-Mn at 2.71 - 2.77 Å
PS II S1 State
Selective X-ray Absorption Spectroscopy
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Photon-in Photon-out X-ray Spectroscopy
technique experimental procedure
x-ray Raman scattering (non resonant)
selective x-ray absorption scan of scan of monochromatormonochromator, analyzer fixed, analyzer fixed
x-ray emission (non resonant) scan of analyzer, monochromator fixed
resonant inelastic x-ray scattering scan of both
monochromator
sampledetector
tunable analyzer
∆E ~ 1 eV
∆E ~ 1 eV
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Principle of RIXS (1s,2p)
Tota
l Ene
rgy
hν = ωhν = Ω
Ω − ω
ground state
intermediate states
final states
K-edge
1s 3dexcitation
2p 1sdecay
1s23dn
1s3dn+1
2p53dn+1
state diagram
48 49 50 51 52 538
9
10
11
12
13
Incident Energy [eV]
Ener
gy T
rans
fer [
eV]
ΓK
ΓL
ener
gy t
rans
fer
Ω −
ω
excitation energy Ω
excitation e
nergy Ω[eV]
energy transfer Ω-ω [eV]
RIXS plane
Mn(II)
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-isolate LUMO resonances (3d) → orbital population, local symmetry
- L-edge like information → sensitivity to spin
- less lifetime broadening- less radiation damage than L-edge
Why RIXS?
Incident Energy [eV]8328 8330 8332 8334 8336
(d)
example 2: high-spin Ni(III)
Glatzel et al, JACS comm, 124, 9668, 2002
RIXS plane
CET versus K-edge XANES CIE versus L-edge XANES
8326 8328 8330 8332 8334 8336 8338
848
850
852
854
856
858
860 hs-Ni(II)
8330 8332 8334 8336 8338 8340 8342
852
854
856
858
860
862
864
ls-Ni(II)
example 1: low spin/high-spin Ni(II)
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E: MnII(acac)2(H2O)2 F: MnIII(acac)3 G: MnIV(sal)2(bipy)
Glatzel et al, JACS, submitted
RIXS Spectra of Mn models and PSII
1st moment positions
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• XRS: low Z systems, non dipole DOS, EXAFS possible
• XES: spin state, chemical state, neighbor distance and type
• S-XAS: extended k-range, chemical/spin specificity
• RIXS: isolate LUMO resonancesL-edge/M-edge like information with hard x-rays
Conclusions
Future
• better resolution, more efficient spectrometers• lots of photons
planned ‘Advanced Spectroscopy and Inelastic Scattering Facility’at SPEAR3, first workshop see:http://www-ssrl.slac.stanford.edu/conferences/ssrl30/IXS_report.pdf
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End of Show
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Comparison of Mn(II), Mn(III) and Mn(IV) 1s,2p RIXS