School On Synchrotron and Free-Electron-Laser Sources and Their Multidisciplinary Applications

2139-15
School on Synchrotron and Free-Electron-Laser Sources and their

Multidisciplinary Applications
26 April - 7 May, 2010
X-ray absorption spectroscopy
F. De Groot
Utrecht University
Netherlands
X-ray Absorption Spectroscopy

(K edges)
Frank de Groot
Studie: scheikunde in Nijmegen (1982-1986)
Promotie: vaste stof chemie Nijmegen (1991)
Interaction of X-rays with matter
Post-doc: Laboratoire pour l utilisation du rayonnement
XANES and EXAFS
lectromagntique in Parijs (93-94)
XANES analysis
Pre-edge analysis
Resonant Inelastic X-ray Spectroscopy (RIXS)
Post-doc: vaste stof natuurkunde in Groningen (95-98)

Universitair hoofddocent: anorganische chemie Utrecht
- Theorie van rntgenspectroscopie
- Ontwikkelen nieuwe rntgenspectroscopien
- Onderzoek aan heterogene katalysatoren
- Onderzoek aan vaste stoffen
Why XX-ray Absorption?
What do we learn from XAS?
Element specific
Metal valence during synthesis and reaction
Sensitive to low concentrations
Metal coordination
(0.01-0.1 %)
Applicable under extreme conditions

(high-pressure, high temperature, in-situ)
Applicable to gasses, liquids and solids

Combination with microscopy
(very small) nanoparticles/clusters
Metal site symmetry

d-band occupation
(3d, 4d or 5d; metal versus oxide, valence)
Energy positions of empty bands of adsorbates

(CO, H2 on Pt, nature of adsorption site)
20 nm spatial-resolved, 50 ps time-resolved
Interaction of xx-rays with matter 1
The photon moves towards the atom
The photon meets an electron and is annihilated
The electron gains the energy of the photon

and is turned into a blue electron.
The blue electron (feeling lonely) leaves the atom

and scatters of neighbors
or escapes from the sample
Interaction of xx-rays with matter
The probability of photon annihilation determines

the intensity of the transmitted photon beam
I0
Ek
Interaction of xx-rays with matter

Energy Spectroscopy
Direction Structure
Polarization Magnetism
100
XAFS studies
photoelectric
absorption
Elastic
scattering
(Thompson)
Inelastic
scattering
(Compton)
Mn
Photoelectric
10
Thom pson
Com pton
1
100
1k
10k
Energy (eV)
100k
X-ray absorption and XX-ray photoemission

Excitation of core electrons to empty states.
I(,k,q)
Spectrum given by the Fermi Golden Rule
I(,k,q)
I(Ek,k,)
I XAS ~ f f T1 i
E f Ei !
I(FIXED)
X-ray absorption
X-ray absorption
ln
I0
= c l
It
= 1x ln
X-ray absorption of an atom
I0
It
Lambert-Beer
= absorption coefficient
x = sample thickness
Measure x-ray intensity
before and after sample
X-ray absorption of a molecule
The molecular orbitals of CO
The molecular orbitals of CO
X-ray absorption
X-ray absorption
X-ray absorption
(single particle interpretation)
Density of States (DOS) is the

integral over k-space of the
band structure.
Core states have no dispersion.
(name Golden Rule given by Fermi; rule itself given by Dirac)
XAS preserves momentum (k)
I XAS ~ f f e r i
Ei !
X-ray absorption
2p
2s
Phys. Rev. B.
40, 5715 (1989) / 48, 2074 (1993)
X-ray absorption
Electronic Structure
Phys. Rev. B.
40, 5715 (1989)
X-ray absorption: core hole effect

TiSi2
Final State Rule:

Spectral shape of XAS
looks like final state
DOS
Initial State Rule:
Intensity of XAS is given
by the initial state
Phys. Rev. B.
41, 11899 (1991)

!
!

"

#

Luitz et al. EPJ B.

21, 363 (2001)
Nyberg et al. Phys. Rev. B.

60, 7956 (1999)
Taillefumier et al. Phys. Rev. B.

66, 195107 (2002)
(HERFD) K edge XANES
K edge XANES
Element specific DOS

L specific DOS
Dipole selection rule (L= 1)
XANES: qualitative analysis
Edge position gives valence

Pre-edge gives valence
Different slopes
Wong et al.
Phys. Rev. B. 30, 5596 (1984)
Spectral Sharpening
K detected XANES
Normal XANES
Pre-edge intensity gives site symmetry
Sharpened prepre-edge analysis
Sharpened prepre-edge analysis
MnZSM-5 (calcined, RT)
MnZSM-5 (heated to 250C)
0.40
0.40
4-fold
Integrated Intensity (norm.)
4-fold
0.35
0.30
3+
2+
Mn
Mn
0.25
0.20
0.15
6-fold
0.10
6539.5
6540.0
6540.5
6541.0
6541.5
0.35
0.30
0.15
6-fold
6540.0
MnZSM-5 (oxidation with N2O)

3+
Mn
0.25
0.20
0.15
6-fold
6540.5
6541.0
Center Energy (eV)
6542.0
4-fold
0.30
6540.0
6541.5
0.40
4-fold
0.35
0.10
6539.5
6541.0
MnZSM-5 (NO treatment)
0.40
Mn
6540.5
Center Energy (eV)
Center Energy (eV)
2+
Mn
0.20
0.10
6539.5
6542.0
3+
2+
Mn
0.25
6541.5
6542.0
0.35
0.30
3+
2+
Mn
Mn
0.25
0.20
0.15
6-fold
0.10
6539.5
6540.0
6540.5
6541.0
6541.5
6542.0
Center Energy (eV)
L edge of 5d-systems > number of empty 5d states

Difference between 5d3/2 and 5d5/2
What do we learn from XANES?

K pre-edge center gives valence
K pre-edge intensity gives site symmetry
L edge intensity gives empty d-states
HERFD-XANES gives details anti-bonding
bands of adsorbates

Difference between metal and oxide
Pre-edges structures in 1s XAS

1s1 3dN 4p1
3dN 4p0

1s1 3dN 4p1
edge
3dN 4p0
1s1 3dN+1 4p0
edge
pre-edge
Pre-edge
and edge
Pre-edges
structures
in 1s XAS
CoIII(acac)
K pre-edge
TM oxides
(LiCoO
Pre-edgesof
structures
in 1s
XAS 2)
1
Co K edge of LiCoO2
edge
low-spin CoIII
3d6 [1A1]
T2g full
Eg empty
pre?
edge
low-spin CoIII
3d6 [1A1]
T2g full
Eg empty
0
7710
7715
7720
7725
Energy (eV)
K pre-edge
TM oxides
(LiCoO
Pre-edgesof
structures
in 1s
XAS 2)
Co K edge of LiCoO2
edge
pre?
edge
low-spin CoIII
3d6 [1A1]
T2g full
Eg empty
0
7710
7715
7720
7725
Energy (eV)
Selective XAFS

Mn 4p
Mn 3d
O 2p
O 2s
20
3d5
MnO
K1,3
Mn 3p 45
Mn 3s
K'
80
O 1s
530
Mn 2p
650
Mn 2s
770
Mn 3p
K2,5
K''
O 2s
6460
Mn 1s 6540
6480
6500
6520
O 2p
6540
6560
Energy [eV]
10
K edgestructures
and 1s2pinRIXS
Pre-edges
1s XAS
K pre-edge
of TM in
oxides
Pre-edges
structures
1s XAS
CoIII(acac)
low-spin CoIII
3d6 [1A1]
T2g full
Eg empty
Vanko et al. (submitted)
K pre-edge
TM oxides
(LiCoO
Pre-edgesof
structures
in 1s
XAS 2)

LiCoO2
Co K edge of LiCoO2
edge
pre?
edge
low-spin CoIII
3d6 [1A1]
T2g full
Eg empty
Co 1s > p DOS
7710
7715
7720
7725
Energy (eV)
Juhin et al. (submitted)
Pre-edges structures in
1s XAS
K pre-edge
of TM in
oxides
Pre-edges
structures
1s XAS
LiCoO2
J. Phys. Cond. Matt. 21, 104207 (2009)
11
Pre-edges structures in
1s XAS
LiCoO2
K pre-edge
of TM in
oxides
Pre-edges
structures
1s XAS
1s1 3dN 4p1
Non-localstructures
screening
Pre-edges
in peaks
1s XAS
1s1 3dN 4p1
edge
edge
1. High valence = strong overlap

2. Metal ion neighbours (M-O-M angle)
3. Metal ion has inversion symmetry
1s13dN
4p(3d-band)
3dN 4p0
non-local
dipole
1s1 3dN+1 4p0 pre-edge

J. Phys. Cond. Matt. 21, 104207 (2009)
Valence selective XAFS

Independent XANES and EXAFS spectra for different
valences in the same system.
1s13dN
4p(3d-band)
non-local
1s1 3dN+1 4p0 pre-edge
3dN 4p0
J. Phys. Cond. Matt. 21, 104207 (2009)

Chemical Dependence of K Emission
Experiment
Theory
Use chemical shift in the XES emission line with <1 eV

resolution.
1s3p decay gives clearest chemical shifts due to
changing 3p3d exchange with 3d-count.
Note: the center-of-gravity does not shift with valence
because the energy difference between 1s and 3p
core levels is constant
Equal center-of-gravity energies used in calculations!
12
HERFDHERFD-XANES
measure deep core hole XANES with the resolution of
a shallow core hole
For example 3d metal K edges, 5d metal L edges and
rare earth L edges.
(1) detect adsorbates on Pt or Au,
(2) separate pre-edges from edges
(3) make quadrupole peaks visible.
The overall resolution should be as good as the
shallow core hole, ~0.3 eV.
(HERFD = High-Energy Resolution Fluorescence Detection)
Inorg.
Inorg. Chem.
41, 3121 (2002)
HERFDHERFD-XANES
Recent data on Pt catalyst with and without CO

(Olga Sofanova, Moniek Tromp et al, Southampton, subm.)
13
X-ray absorption

(L edges)
I XAS ~ f f e r i
Oxygen K edge
Ei !
2p
2s
Phys. Rev. B.
40, 5715 (1989) / 48, 2074 (1993)
Oxygen K edge

Fermi Golden Rule:
IXAS = |<f|dipole| i>|2 [E=0]
Single electron (excitation) approximation:
IXAS = |<empty|dipole| core>|2
1. Neglect <vv|1/r|vv> (many body effects)

2. Neglect <cv|1/r|cv> (multiplet effects)
multiplet effects
2p XX-ray absorption
Strong overlap of core and valence

wave functions
3d
<2p3d|1/r|2p3d>
Single Particle model breaks down

2p3/2
2p1/2
I XAS ~ 2 p 5 3d 6 e r 3d 5
Ei !
DFT:
Single Particle:
1s edges
1s edges
Multiplets:
No Unified
Interpretation!
2p, 3s, 3p edges
(WIEN, FEFF, GN-XAS

..)
Multiplets:
2p, 3s, 3p edges
(TT-MULTIPLETS)
2p XAS of TiO2
Charge Transfer Multiplet program

Ti4+
Used for the analysis of XAS, EELS,

Photoemission, Auger, XES,
Put Ti4+ in Ion

Set Autoplot ON
Press Run
ATOMIC PHYSICS
GROUP THEORY
MODEL HAMILTONIANS
Atomic Multiplet Theory
Atomic Multiplet Theory
=E
H = 2pmi + Ze
+
ri
2
pairs
=E
e2
rij
+ (ri ) l i si
N
H = 2pmi + Ze
+
ri
2
X
N
Kinetic Energy
Nuclear Energy
Electron-electron interaction
Spin-orbit coupling
Atomic Multiplet Theory (ground state)

2 S +1
LJ | re12 |2 S +1LJ = f k F k + g k G k
2
pairs
e2
rij
pairs
e2
rij
+ (ri ) l i si
N
Kinetic Energy
Nuclear Energy
Electron-electron interaction
Spin-orbit coupling
Atomic Multiplet Theory (core hole)

2 S +1
LJ | re12 |2 S +1LJ = f k F k + g k G k
2
Electron Correlation of Valence States
H ATOM =
Core Valence Overlap
+ (ri ) li si
H ATOM =
pairs
Valence Spin-orbit coupling
e2
rij
+ (ri ) li si
N
Core Spin-orbit coupling
Multiplet Effects
2p XAS of TiO2
Ti4+
1s
0.07
2s
2p
3s
13
3p
Put Ti4+ in Ion

Set Autoplot ON
Press Run
17
Core Valence Overlap
17
Core Spin-orbit coupling
2p XAS of TiO2
Ti4+
2p XAS of TiO2
Ti4+
CTM4XAS:
Error for 3d0 systems in
version 3
Put Ti4+ in Ion

Set Autoplot ON
Suppress Sticks ON
Use version 2.5 for

3d0 systems
(Will be solved in
version 3.1)
Term Symbols
Term symbols of a
3P0
1P 3P ,
1
1
3D
1
2p53d1
3x3
configuration
1.0
3P
2
1D 3D
2
2
3F
2
[1
Atomic multiplets
4
4x5
Ti4+
1.0
1.0
3D
3
Slater integral reduction:
1F 3F
3
3
3F
4
1]
1
3x7
1x9
The Fdd, Fpd and Gpd Slater integrals

can be reduced to any other value.
The default value is 1.0 which implies
atomic values.
Ground state: 3d0: L=S=J=0 1S0

Selection rule: Final state must have J
J=1
2p XAS of TiO2
Ti4+
0.5 0.5
2p XAS of TiO2
Ti4+
0.5
0.0 0.0
Put Ti4+ in Ion

Set Autoplot ON
Set Expert options
ON
Add 40 40 40 for
Fdd, etc.
0.0
Put Ti4+ in Ion

Set Autoplot ON
Set Slater integral
reduction to 0.0
3d0 XAS calculation
2p XAS of TiO2
Ti4+
0.0 0.0
0
0.0

0.0

3dN XAS calculation
Hunds rules

Term symbols with maximum spin S are lowest in energy,

Among these terms:

Term symbols with maximum L are lowest in energy

In the presence of spin-orbit coupling, the lowest term has

J = |L-S| if the shell is less than half full

J = L+S if the shell is more than half full

!
3d1 has 2D3/2 ground state

3d9 has 2D5/2 ground state
3d2 has 3F2 ground state

3d8 has 3F4 ground state
Give the Hunds rule ground states for 3d1 to 3d9
Term Symbols and XAS

Fe atom:
Ground state:
3d6 (4s2) 5D j=4
!


Fe atom:
Ground state:
Final state:
Dipole transition:
3d6 (4s2)
2p53d7
p-symmetry
5D, etc.
3d6-configuration:
2p53d7-configuration: 110 states
1P
p-transition:
ground state symmetry: 5D

5D 1P = 5PDF
transition:
possible final states:
j=4
j= 3,4, 5
j=+1,0,-1
5D
4
68 states
Exercise
Calculate the atomic multiplet spectrum of the 2p

XAS spectrum of an iron atom (use Fe2+)
Fe atom:
Ground state:
3d6 (4s2) 5D j=4
Run CTM4XAS with Autoplot ON.

Do a second calculation with the 3d spin-orbit
coupling set to zero.
Choose an appropriate name;

the program saves the rcn, rcg, rac, ban, plo and
xy files with this name.
2p XAS of NiO
5D
0
5D
5D
4
Ni2+
Put Ni2+ in Ion

Set Autoplot ON
NiII ion in NiO:

Ground state:
Final state:
Dipole transition:
3d8-configuration:
2p53d9-configuration:
p-transition:
3d8
2p53d9
p-symmetry
1S 1D, 3P,1G, 3F
,
2P2D = 1,3PDF
1P
ground state symmetry: 3F

3F 1P = 3DFG
transition:
two possible final states: 3D, 3F
3d XAS of La2O3
""# $ $ "% &
'
(
j=4
j=0,1,2,3,4
j=+1,0,-1
3F
4
3D ,3F ,3F 1 F
3
3
4,
3
3d XAS of La2O3
&
),,,
,-
),,,
,-.
' ((
' Transition </01%/),),2
'
&
' 34 $
' &)*+

' ),,,
,- ),,,
,-.
3d XAS of La2O3
3d XAS of La2O3
Thole et al.
PRB 32, 5107 (1985)
3d XAS of Nd
Crystal Field Effects

eg states
NdIII ion in Nd metal

Ground state: 4f3
Final state: 3d94f4
t2g states
Thole et al.
PRB 32, 5107 (1985)
2p XAS of TiO2
Octahedral crystal field splitting

Ti4+
metal ion
in free space
in symmetrical field
in octahedral ligand field
eg
Put Ti4+ in Ion

Set Autoplot ON
Press Run
x2-y2 z2
t2g
yz
xz
xy
x2-y2 yz z2 xz xy
2p XAS of TiO2
Crystal Field Effects in CTM
Ti4+
Crystal field effect:

+ 2.5 for 10Dq
+ Split ON
+ 0.5 Lorentzian L2
+ 467 split energy
2.5
7 = 2.13 eV
0.5
467
Crystal Field Effects

#
Crystal Field Effect on XAS
#4563 7
8

9%
8%%
8%9%%
J in SO3
Deg.
Branchings
in Oh
Deg.
A1
A1
3T1
A2
4E, 4T2
T1
3A2, 3T1,3T2
T2
A1, E, T1, T2
12
Deg.
Branchings
A1
3T1
4E, 4T2
3A2, 3T1,3T2
A1, E, T1, T2
12
<1S0|dipole|1P1> goes to <A1|T1|T1>
Effect of 10Dq on XAS:3d0
Crystal Field Effect on XAS
J in SO3
25
<1S0|dipole|1P1> goes to <A1|T1|T1>
Comparison with Experiment
2p XAS of TiO2
Ti4+
0.0 0.0 0.0
2.5
0.5
467
Turning multiplet effects off
Effect of 10Dq on XAS:3dN
High-spin or Low-spin
V3+
10Dq > 3J
(d4 and d5)
1.5
10Dq > 2J
(d6 and d7)
2p XAS of Mn2+
2p XAS of Mn2+
Mn2+
High-spin: 10Dq =
1.2
Low-spin: 10Dq =
3.0
1.2
2p XAS of Mn2+
3d spin-orbit coupling
Effect of 10Dq on XAS:3dN
Crystal Field Multiplets

1
3d82p53d9
Normalized Intensity
Ni2+, cubic field

neglect 2p s
neglect 4sp, O2p
0
850
855
860
865
Energy (eV)
870
10
Metal L edges
5
3d
Normalized Intensity
Exercise
3d
2
3d
3d
4
3d
3d
6
3d
3d
8
3d
Calculated L-edges
3dN2p53dN+1
Calculate the crystal field multiplet spectrum of

the 2p XAS spectrum of all divalent transition
metal ions from Ca to Cu. Use 10Dq=1.2 eV.
Single configuration
Atomic values for
intra-atomic interactions
Cubic crystal field of 1.2 eV
Run CTM4XAS with Autoplot ON.

Do a calculation with and without the 3d spin-orbit
coupling set to zero.
3d
Which TM2+ ions are sensitive to 3d spin-orbit

coupling? Explain
-6 -4 -2 0 2 4 6 8 10 12 14 16
Relative Energy (eV)
Exercise
2p XAS of CoO
Co2+
Calculate the crystal field multiplet spectrum of

the 2p XAS spectrum of all divalent transition
metal ions from Ca to Cu.
0.0
+ with and without

3d spin-orbit (1.0
and 0.0)
1.2
Use 10Dq=1.0, 2.0 and 3.0 eV.

Which TM2+ ions are very sensitive to the crystal
field strength? Explain
Charge Transfer Effects
MnO: Ground state: 3d5 + 3d6L

Energy of 3d6L: Charge transfer energy
3d6L
3d5
2p53d7L
+U-Q
2p53d6
Ground state of a transition metal system

3dN at every site
Charge fluctations
11
Hubbard U for a 3d8 ground state:

U= E(3d7) + E(3d9) E(3d8) E(3d8)
Ligand-to-Metal Charge Transfer (LMCT):
= E(3d9L) E(3d8)

2+U
3U-2
15
Energy (eV)
Energy (eV)
15
Charge Transfer Effects in XAS
10
U-
+U-Q
10
10
Charge Transfer Effects in XPS
10
Charge transfer effects in XAS and XPS

Transition metal oxide: Ground state: 3d5 + 3d6L
15
Energy (eV)
3d6L
XPS
10
-Q
2p53d5
3d5
XAS
-Q
Ground State
2p53d7L
+U-Q
2p53d6L
6
2p53d6
10
12
2p XAS of Ni2+
Ni2+
2.0
6.0
7.0
1.0
Charge Transfer Effects in XAS

NiO: Ground state: 3d8 + 3d9L
3d9L
Charge Transfer Multiplets of Ni2+

=3
=9
=0
=6
Spectral shape:
(1) Multiplet effects
(2) Charge Transfer
2p53d10L
+U-Q
2p53d9
3d8
Charge transfer
J. Elec. Spec.
67, 529 (1994)
Exercise
13
Exercise
Try to reproduce the Cu 2p XAS spectrum of Cs2KCuF6
The symmetry is octahedral;
Use T(eg) = 2.0, T(eg)=2* T(t2g) and Udd-Upd=-1.0 eV.
Optimize 10Dq and .
Exercise
Try to reproduce the Cu 2p XAS spectrum of Cs2KCuF6
The symmetry is octahedral;
Use T(eg) = 2.0, T(eg)=2* T(t2g) and Udd-Upd=-1.0 eV.
Optimize 10Dq and .
Try to reproduce the Cu 2p XAS spectrum of

La2Li1/2Cu1/2O4
The symmetry is square planar;
Use Ds=0.3, T(b1) = 3.0, T(a1) = 1.73, T(b2) = 1.5, T(e) =
1.05* and Udd-Upd=-1.0 eV.
Optimize 10Dq and .
Exercise
Try to reproduce the Cu 2p XAS spectrum of
La2Li1/2Cu1/2O4
The symmetry is square planar;
Use Ds=0.3, T(b1) = 3.0, T(a1) = 1.73, T(b2) = 1.5, T(e) =
1.05* and Udd-Upd=-1.0 eV.
Optimize 10Dq and .
Exercise
Calculate all spectra for NiO
2p XAS, 3p XAS, 1s (pre-edge) XAS

1s, 2s and 3s XPS
2p and 3p XPS
1s2p and 1s3p XES
X-MCD
Cu2+: 3d9
X-MCD
14
Exercise
X-MCD
MCD
mJ=-5/2
to
mJ=-3/2
MCD
no LS
Run CTM4XAS for Cu2+ in C4 symmetry, with a

magnetic field (M) of 1 meV; Plot the XAS spectrum
and the MCD spectrum;
Run CTM4XAS for Cu2+ in C4 symmetry, with a
magnetic field (M) of 1 meV and with the 3d spin-orbit
coupling set to 0.0; Plot the XAS spectrum and the
MCD spectrum;
Exercise
Run CTM4XAS for Cu2+ in C4v symmetry, with a
magnetic field (M) of 1 meV, adding a crystal field
value 10Dq of 0.3 eV.; Plot the XAS spectrum and the
MCD spectrum;
Perform a number of calculations for varying values of
10Dq, in steps of 0.3 eV from 0.0 to 1.5 eV. What
does one observe for the XAS and MCD spectra?
X-MCD
MCD
no LS
MCD
+ crystal field
Perform a calculation for negative values of 10Dq, for

example -0.3, -0.5 and -0.9 eV. What does one
observe? Explain.
RIXS
RIXS
Butorin
J. Elec. Spec 110, 213 (2000)
15
Resonant Inelastic XX-ray Spectroscopy

2p XAS of CaF2
Resonant Inelastic XX-ray Scattering

2p3s RIXS of CaF2
3d0
3d0
2p53d1
2p53d1
3s13d1
3s13d1
Resonant Inelastic XX-ray Spectroscopy
Phys. Rev. B.
53, 7099 (1996)
Soft xx-ray RIXS and magnetism

NiII 3d8 [] 2p53d9[jj] 3d8[]
Butorin
J. Elec. Spec 110, 213 (2000)

S
spin-flip
dd
MS
spin-flip
3p3d RIXS
of Sr2CuO2Cl2
x2-y2
xz
2p3d RIXS of NiO
Phys. Rev. B.
57, 14584 (1998)
New exp: EPFL
xy
z2
0 3p 0 + dd + spin-flip
Phys. Rev. Lett.

Lett.
80, 5204 (1998)
16
Effect of energy resolution (on CoO)

Pre-edgeCoO
and edge
high-spin CoII
3d7 [4T2]
Only quadrupole peaks visible

3d7 1s13d8 2p53d8
Only correct with interference effects ON
Pre-edge and edge
Non-local
peaks
RIXS-MCD screening
at the K pre-edge
CoII(acac)
LiCoO2
AgCoO2
LaCoO3
at 20K
Vanko et al.
(submitted)
Non-local
peaks
RIXS-MCD screening
at the K pre-edge
Non-local
peaks
RIXS-MCD screening
at the K pre-edge
17
Non-local
screening
peaks
RIXS-MCD
at the
K pre-edge
of Fe3O4
Non-local
peaks
RIXS-MCD screening
at the K pre-edge
Non-local
peaks
RIXS-MCD screening
at the K pre-edge
La 2p XAS: effects of HERFD

2p5d dipole
2p4f quadrupole
XMCD at high-pressure
Glatzel et al. PRB 72, 014117 (2005)
HERFD makes prepre-edge 2p4f transition visible

LaF3
2p5d dipole
2p4f quadrupole
Suljoti et al. (new data from ID26)
18
Does FY does measure X-ray Absorption?
2p5d dipole
LaF3
2p4f quadrupole
HERFD makes prepre-edge 2p4f transition visible

Why has the 2p4f prepre-edge 3 peaks?
?
?
Does HERFD measure X-ray Absorption?
2p4d RIXS of LaF3
2p4f quadrupole
4f0 2p5 4f1
4f0 + 4f1L 2p5 4f1 + 2p5 4f2L

4f05d0 + 4f0 5d1L 2p5 4f1 + 2p54f15d1L
HERFD-XANES of LaF3
2p4d RIXS of LaF3

measured with 2p4d XES
4f0 2p5 4f1 4d9 4f1
one peak
multiplet structure
19
CTM4XAS
CTM4XAS simulations
Applications
2p XAS of Mn2+ and Fe3+

High-spin: 10Dq = 1.2
MnO
Low-spin: 10Dq = 3.0
FeIII(tacn)
Systems with pi-bonds

X-MCD of Fe-complexes on metal surfaces
In-situ STXM chemical imaging
CTM4XAS simulations
XAS
orbitalCovalence
covalence
XASand
anddifferential
Differential Orbital
Derive DOC from CTM4XAS simulation
Comparison to DOC from DFT (ADF) calculation
FeIII(tacn)2
Eg (63%)
T2g ( 99%)
J. Phys. Chem. B. 109, 20751 (2005)
LMCT and MLCT: - bonding
XAS and Differential Orbital Covalence

Derive DOC from CTM4XAS simulation
Comparison to DOC from DFT (ADF) calculation
FeIII: Ground state: 3d5 + 3d6L
3d6L
with Ed Solomon (Stanford) JACS 125, 12894 (2003),

JACS 128, 10442 (2006), JACS 129, 113 (2007)

3d5
2p53d7L
+U-Q
2p53d6
JACS 128, 10442 (2006), JACS 129, 113 (2007)
20
3d6L
2p53d5L
3d4L
-U+Q + 2
3d6L
2p53d7L
+U-Q - 2
2p53d6
3d5

JACS 128, 10442 (2006), JACS 129, 113 (2007)
Fe(TPA)
4 on Cu(100)
Supramolecular
Pietro
previous withnext
Pietro
previous withnext
control of Fe arrays
Gambardella (Barcelona), Nature Materials 8, 189 (2009)
Fe(TPA)
4 on Cu(100)
Supramolecular
3d4L
FeIII(tacn)2
10
Normalized Absorption
FeIII: Ground state:
3d5
Fit X
Series2
FeIII(CN)6
6
4
2
0
700
-2
705
710
715
720
725
730

Energy (eV)
JACS 128, 10442 (2006), JACS 129, 113 (2007)
Fe(TPA)
4 on Cu(100)
Supramolecular
Pietro
previous withnext
Fe(TPA)
4 on Cu(100)
Supramolecular
Pietro
previous withnext
21
Electron Energy Loss Spectroscopy
Why X-ray absorption?
Identical spectral shape
Element specific
Low concentrations (0.01-0.1 wt%)
XAS at Synchrotron
EELS with Electron
Microscope
Valence, Spin-state,
Crystal field energies, dd-excitations
Hybridization (differential orbital covalence)
MO energies / Density of states
XAS: 0.2 eV/20nm

EELS: 0.2 eV/0.5 nm
UHV
XAS: extreme
conditions
Space?, Time?, Pressure?
EELS: vacuum
Electron Energy Loss Spectroscopy
TEMTEM-EELS of FeZSMFeZSM-5
1.0
fe4
Y Axis Title
0.8
0.6
0.4
0.2
0.0
700
705
710
715
720
725
X Axis Title
730
180000
Y Axis Title
160000
140000
120000
100000
80000
60000
530
535
540
545
550
555
560
565
570
X Axis Title

Quantify EELS spectra of Ti, Mn and Co
10nm
J. Catal.
230, 301 (2005)
22

Before reduction
(Co,Mn)3O4 particles
After reduction
Co metal +
MnO particles
PCCP 7, 568 (2005)
J. Catal. 230, 301 (2005)
SPACE: Electron Energy Loss in a TEM

Co(Mn)Ox
MnMn-doped Co on TiO2
TiO2
+H2
10 nm
SPACE: STEM-EELS versus STXM-XAS

STEMSTEM-EELS
STXMSTXM-XAS
UHV, 0.5 nm
1 bar, 500C, 30 nm
Co L edge at
each pixel
(0.5nm2)
780
785
790
795
Energy (eV)
Fernando Morales et al., PCCP 7, 568 (2005); J. Catal. 230, 310 (2005)
Metal L edges in 1989 and 2009

1989
UHV
RT
bulk
Fischer-Tropsch Synthesis
2009
2 bar flowing gas

up to 750K
20 nm resolution
-The Fischer-Tropsch GTL process produces an

extremely clean synthetic fraction of gasoil
- GTL fuel is virtually free of sulphur and aromatics.
23
Nanoscale chemical imaging of a working catalyst
On reactor cell: Fredrik Creemer et al. Ultramicroscopy 108, 993 (2008)
Emiel de Smit et al. Nature 456, 222 (2008); Angew. Chem. 48, 3632 (2009)
STXM of Fe nanoparticles on TiO2
On reactor cell: Fredrik Creemer et al. Ultramicroscopy 108, 993 (2008)
Fe3O4
Fe3O4
1 bar H2
150 C
1 bar H2
250 C
24
SiO2
Oxygen K-edge
530
540
550
X-Ray Photon Energy (eV)
Nanoscale chemical imaging of Fe2O3 [K, Cu]/SiO2
Iron L-edge
Fe2O3
; :
705
710
715
720
725
X-Ray Photon Energy (eV)
; #
; :
-
;
:#-
; :
5 #7
:
#
K+Cu doped Fe2O3 on SiO2
K+Cu doped Fe3O4 on SiO2
Before and after reduction
Before and after FTS

25
Why X-ray Absorption?

Element specific
Low concentrations (0.01-0.1 wt%)
Valence, Spin-state, Crystal field energies

Hybridization, MO energies / Density of states
Time: excited states (mainly) in ps range

Pressure: 1 bar/500 C flowing gas
Space: 0.5 nm (STEM), 20 nm (STXM)
www.anorg.chem.uu.nl/people/staff/FrankdeGroot/
26

School On Synchrotron and Free-Electron-Laser Sources and Their Multidisciplinary Applications

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2139-15

School on Synchrotron and Free-Electron-Laser Sources and their

26 April - 7 May, 2010

X-ray absorption spectroscopy

X-ray Absorption Spectroscopy

Interaction of X-rays with matter

Post-doc: Laboratoire pour l utilisation du rayonnement

XANES and EXAFS

lectromagntique in Parijs (93-94)

Post-doc: vaste stof natuurkunde in Groningen (95-98)

Why XX-ray Absorption?

What do we learn from XAS?

Metal valence during synthesis and reaction

Sensitive to low concentrations

Applicable under extreme conditions

Applicable to gasses, liquids and solids

(very small) nanoparticles/clusters

Metal site symmetry

Energy positions of empty bands of adsorbates

Interaction of xx-rays with matter 1

Interaction of xx-rays with matter 1

The photon moves towards the atom

The photon meets an electron and is annihilated

Interaction of xx-rays with matter 1

Interaction of xx-rays with matter 1

The electron gains the energy of the photon

The blue electron (feeling lonely) leaves the atom

Interaction of xx-rays with matter 1

Interaction of xx-rays with matter

The probability of photon annihilation determines

Interaction of xx-rays with matter

X-ray absorption and XX-ray photoemission

X-ray absorption and XX-ray photoemission

X-ray absorption and XX-ray photoemission

X-ray absorption of an atom

X-ray absorption of a molecule

The molecular orbitals of CO

The molecular orbitals of CO

Excitation of core electrons to empty states.

Spectrum given by the Fermi Golden Rule

Density of States (DOS) is the

(name Golden Rule given by Fermi; rule itself given by Dirac)

XAS preserves momentum (k)

X-ray Absorption Spectroscopy

X-ray absorption: core hole effect

Final State Rule:

"        

   

Luitz et al. EPJ B.

Nyberg et al. Phys. Rev. B.

Taillefumier et al. Phys. Rev. B.

(HERFD) K edge XANES

Element specific DOS

XANES: qualitative analysis

Edge position gives valence

XANES: qualitative analysis

XANES: qualitative analysis

Edge position gives valence

XANES: qualitative analysis

Edge position gives valence

XANES: qualitative analysis

Pre-edge intensity gives site symmetry

Sharpened prepre-edge analysis

"