F. De Groot
Utrecht University
Netherlands
Frank de Groot
Studie: scheikunde in Nijmegen (1982-1986)
Promotie: vaste stof chemie Nijmegen (1991)
XANES analysis
Pre-edge analysis
Resonant Inelastic X-ray Spectroscopy (RIXS)
Element specific
Metal coordination
(0.01-0.1 %)
I0
Ek
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
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
I0
It
Lambert-Beer
= absorption coefficient
x = sample thickness
Measure x-ray intensity
before and after sample
X-ray absorption
X-ray absorption
X-ray absorption
(single particle interpretation)
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)
Electronic Structure
Phys. Rev. B.
41, 11899 (1991)
!
!
K edge XANES
Spectral Sharpening
K detected XANES
Normal XANES
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
3+
Mn
0.25
0.20
0.15
6-fold
6540.5
6541.0
6542.0
4-fold
0.30
6540.0
6541.5
0.40
4-fold
0.35
0.10
6539.5
6541.0
0.40
Mn
6540.5
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
3dN 4p0
edge
3dN 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 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
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
Co 1s > p DOS
7710
7715
7720
7725
Energy (eV)
Pre-edges structures in
1s XAS
K pre-edge
of TM in
oxides
Pre-edges
structures
1s XAS
LiCoO2
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
1s13dN
4p(3d-band)
3dN 4p0
non-local
dipole
1s13dN
4p(3d-band)
non-local
3dN 4p0
Theory
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
13
X-ray absorption
I XAS ~ f f e r i
Oxygen K edge
Ei !
Electronic Structure
2p
2s
Phys. Rev. B.
40, 5715 (1989) / 48, 2074 (1993)
Oxygen K edge
multiplet effects
2p XX-ray absorption
3d
<2p3d|1/r|2p3d>
I XAS ~ 2 p 5 3d 6 e r 3d 5
Ei !
DFT:
Single Particle:
1s edges
1s edges
Multiplets:
No Unified
Interpretation!
Multiplets:
2p, 3s, 3p edges
(TT-MULTIPLETS)
2p XAS of TiO2
ATOMIC PHYSICS
GROUP THEORY
MODEL HAMILTONIANS
=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
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
LJ | re12 |2 S +1LJ = f k F k + g k G k
2
H ATOM =
+ (ri ) li si
H ATOM =
pairs
e2
rij
+ (ri ) li si
N
Multiplet Effects
2p XAS of TiO2
Ti4+
1s
0.07
2s
2p
3s
13
3p
17
17
2p XAS of TiO2
Ti4+
2p XAS of TiO2
Ti4+
CTM4XAS:
Error for 3d0 systems in
version 3
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
1F 3F
3
3
3F
4
1]
1
3x7
1x9
2p XAS of TiO2
Ti4+
0.5 0.5
2p XAS of TiO2
Ti4+
0.5
0.0 0.0
0.0
2p XAS of TiO2
Ti4+
0.0 0.0
0
0.0
0.0
Hunds rules
!
!
3d6 (4s2)
2p53d7
p-symmetry
5D, etc.
3d6-configuration:
2p53d7-configuration: 110 states
1P
p-transition:
j=4
j= 3,4, 5
j=+1,0,-1
5D
4
68 states
Exercise
Fe atom:
Ground state:
2p XAS of NiO
5D
0
5D
5D
4
Ni2+
3d8
2p53d9
p-symmetry
1S 1D, 3P,1G, 3F
,
2P2D = 1,3PDF
1P
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
&
),,,
,-
),,,
,-.
'
&
3d XAS of La2O3
3d XAS of La2O3
Thole et al.
PRB 32, 5107 (1985)
3d XAS of Nd
t2g states
Thole et al.
PRB 32, 5107 (1985)
2p XAS of TiO2
metal ion
in free space
in symmetrical field
eg
x2-y2 z2
t2g
yz
xz
xy
x2-y2 yz z2 xz xy
2p XAS of TiO2
Ti4+
2.5
7 = 2.13 eV
0.5
467
#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
J in SO3
25
2p XAS of TiO2
Ti4+
0.0 0.0 0.0
2.5
0.5
467
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
3d82p53d9
Normalized Intensity
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
Single configuration
Atomic values for
intra-atomic interactions
Cubic crystal field of 1.2 eV
3d
-6 -4 -2 0 2 4 6 8 10 12 14 16
Relative Energy (eV)
Exercise
2p XAS of CoO
Co2+
0.0
1.2
3d6L
3d5
2p53d7L
+U-Q
2p53d6
11
3U-2
15
Energy (eV)
Energy (eV)
15
10
U-
+U-Q
10
10
10
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
3d9L
=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 .
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
X-MCD
Cu2+: 3d9
X-MCD
14
Exercise
X-MCD
MCD
mJ=-5/2
to
mJ=-3/2
MCD
no LS
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
RIXS
RIXS
Butorin
J. Elec. Spec 110, 213 (2000)
15
3d0
3d0
2p53d1
2p53d1
3s13d1
3s13d1
Phys. Rev. B.
53, 7099 (1996)
Butorin
J. Elec. Spec 110, 213 (2000)
dd
MS
spin-flip
3p3d RIXS
of Sr2CuO2Cl2
x2-y2
xz
Phys. Rev. B.
57, 14584 (1998)
New exp: EPFL
xy
z2
0 3p 0 + dd + spin-flip
16
high-spin CoII
3d7 [4T2]
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
XMCD at high-pressure
Glatzel et al. PRB 72, 014117 (2005)
2p5d dipole
2p4f quadrupole
18
2p5d dipole
LaF3
2p4f quadrupole
?
?
2p4f quadrupole
4f0 2p5 4f1
HERFD-XANES of LaF3
one peak
multiplet structure
19
CTM4XAS
CTM4XAS simulations
Applications
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%)
3d6L
3d5
2p53d7L
+U-Q
2p53d6
with Ed Solomon (Stanford) JACS 125, 12894 (2003),
JACS 128, 10442 (2006), JACS 129, 113 (2007)
20
3d6L
2p53d5L
3d4L
-U+Q + 2
3d6L
2p53d7L
+U-Q - 2
2p53d6
3d5
Fe(TPA)
4 on Cu(100)
Supramolecular
Pietro
previous withnext
Pietro
previous withnext
control of Fe arrays
Fe(TPA)
4 on Cu(100)
Supramolecular
3d4L
control of Fe arrays
FeIII(tacn)2
10
Normalized Absorption
3d5
Fit X
Series2
FeIII(CN)6
6
4
2
0
700
-2
705
710
715
720
725
730
Fe(TPA)
4 on Cu(100)
Supramolecular
Pietro
previous withnext
Fe(TPA)
4 on Cu(100)
Supramolecular
Pietro
previous withnext
control of Fe arrays
control of Fe arrays
21
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
UHV
XAS: extreme
conditions
EELS: vacuum
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
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)
MnMn-doped Co on TiO2
TiO2
+H2
10 nm
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)
UHV
RT
bulk
Fischer-Tropsch Synthesis
2009
23
Emiel de Smit et al. Nature 456, 222 (2008); Angew. Chem. 48, 3632 (2009)
Fe3O4
Fe3O4
1 bar H2
150 C
1 bar H2
250 C
Emiel de Smit et al. Nature 456, 222 (2008); Angew. Chem. 48, 3632 (2009)
Emiel de Smit et al. Nature 456, 222 (2008); Angew. Chem. 48, 3632 (2009)
24
SiO2
Oxygen K-edge
530
540
550
Normalized Absorption
Normalized Absorption
Iron L-edge
Fe2O3
;
:
705
710
715
720
725
; #
; :
-
;
:#-
; :
5 #7
:
#
Emiel de Smit et al. Nature 456, 222 (2008); Angew. Chem. 48, 3632 (2009)
Emiel de Smit et al. Nature 456, 222 (2008); Angew. Chem. 48, 3632 (2009)
Emiel de Smit et al. Nature 456, 222 (2008); Angew. Chem. 48, 3632 (2009)
25
www.anorg.chem.uu.nl/people/staff/FrankdeGroot/
26