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Study of magnetic properties of a new vanadate
Cu13Fe4V10O44
Janusz TypekInstitute of Physics West Pomeranian University of Technology
Szczecin Poland
Outline
bull Why new vanadate Cu13Fe4V10O44 bull Sample preparation and chemistry bull Measuring methods dc magnetometry and EPRbull Results of dc magnetization measurementsbull Results of EPR measurementsbull Conclusions about magnetic structure
Why to study Cu13Fe4V10O44
bull Similar compounds from the same system of vanadates have important catalytic propertiesbull Defect structure and grain surface play an important role in catalysisbull Knowledge of magnetic defects and ions may lead to better understanding of the mechanism of the catalytic processes
Sample preparation
025 050 075 100
025
050
075
100
025
050
075
100
mol
of CuO
mol
o
f V2
O 5
mol of Fe2O3
Fe2O3
CuO
V2O5
13 CuO + 5 V2O5 + 2 Fe2O3 rarr Cu13Fe4V10O44
A Blonska-Tabero J Therm Anal Calorim 110 (2012) 161
Structure ndash possible types
Lyonsite -Cu3Fe4(VO4)6 a new iron-copper vanadate mineral
six isolated VO4 tetrahedraFeO6 octahedra
square-planar CuO4 groups
HowardewansiteMineral NaCuFe2(VO4)3
In figure Mn3Fe4(VO4)6
VO4 FeO6 MnO5 MnO4 polyhedra
EPR and dc magnetometry
Magnetic resonance spectrometerX-band Bruker E 500 (1997)
Magnetic Property Measurements SystemMPMS XL-7 Quantum Design (2011)
Dynamics τ~10-10 s Static τ~1 s
dc magnetization susceptibility study
0 50 100 150 200 250 30020x10-5
40x10-5
60x10-5
80x10-5
10x10-4
12x10-4
2 4 6 8 10 12 14 16 18 2080x10-5
90x10-5
10x10-4
11x10-4
[e
muO
e-1g
-1]
Temperature [K]
01 kOe 1 kOe 10 kOe 70 kOe
[e
muO
e-1g
-1]
Temperature [K]
0 40 80 120 160 200 240 2800
1
2
3
4
5 01 kOe 1 kOe 10 kOe 70 kOe
0 10 20 30 40 5008
10
12
14
16
18
1
[104
em
u-1O
eg
]
Temperature [K]
1
[104
emu
-1O
eg
]
Temperature [K]
dc magnetization reciprocal susceptibility
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
Outline
bull Why new vanadate Cu13Fe4V10O44 bull Sample preparation and chemistry bull Measuring methods dc magnetometry and EPRbull Results of dc magnetization measurementsbull Results of EPR measurementsbull Conclusions about magnetic structure
Why to study Cu13Fe4V10O44
bull Similar compounds from the same system of vanadates have important catalytic propertiesbull Defect structure and grain surface play an important role in catalysisbull Knowledge of magnetic defects and ions may lead to better understanding of the mechanism of the catalytic processes
Sample preparation
025 050 075 100
025
050
075
100
025
050
075
100
mol
of CuO
mol
o
f V2
O 5
mol of Fe2O3
Fe2O3
CuO
V2O5
13 CuO + 5 V2O5 + 2 Fe2O3 rarr Cu13Fe4V10O44
A Blonska-Tabero J Therm Anal Calorim 110 (2012) 161
Structure ndash possible types
Lyonsite -Cu3Fe4(VO4)6 a new iron-copper vanadate mineral
six isolated VO4 tetrahedraFeO6 octahedra
square-planar CuO4 groups
HowardewansiteMineral NaCuFe2(VO4)3
In figure Mn3Fe4(VO4)6
VO4 FeO6 MnO5 MnO4 polyhedra
EPR and dc magnetometry
Magnetic resonance spectrometerX-band Bruker E 500 (1997)
Magnetic Property Measurements SystemMPMS XL-7 Quantum Design (2011)
Dynamics τ~10-10 s Static τ~1 s
dc magnetization susceptibility study
0 50 100 150 200 250 30020x10-5
40x10-5
60x10-5
80x10-5
10x10-4
12x10-4
2 4 6 8 10 12 14 16 18 2080x10-5
90x10-5
10x10-4
11x10-4
[e
muO
e-1g
-1]
Temperature [K]
01 kOe 1 kOe 10 kOe 70 kOe
[e
muO
e-1g
-1]
Temperature [K]
0 40 80 120 160 200 240 2800
1
2
3
4
5 01 kOe 1 kOe 10 kOe 70 kOe
0 10 20 30 40 5008
10
12
14
16
18
1
[104
em
u-1O
eg
]
Temperature [K]
1
[104
emu
-1O
eg
]
Temperature [K]
dc magnetization reciprocal susceptibility
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
Why to study Cu13Fe4V10O44
bull Similar compounds from the same system of vanadates have important catalytic propertiesbull Defect structure and grain surface play an important role in catalysisbull Knowledge of magnetic defects and ions may lead to better understanding of the mechanism of the catalytic processes
Sample preparation
025 050 075 100
025
050
075
100
025
050
075
100
mol
of CuO
mol
o
f V2
O 5
mol of Fe2O3
Fe2O3
CuO
V2O5
13 CuO + 5 V2O5 + 2 Fe2O3 rarr Cu13Fe4V10O44
A Blonska-Tabero J Therm Anal Calorim 110 (2012) 161
Structure ndash possible types
Lyonsite -Cu3Fe4(VO4)6 a new iron-copper vanadate mineral
six isolated VO4 tetrahedraFeO6 octahedra
square-planar CuO4 groups
HowardewansiteMineral NaCuFe2(VO4)3
In figure Mn3Fe4(VO4)6
VO4 FeO6 MnO5 MnO4 polyhedra
EPR and dc magnetometry
Magnetic resonance spectrometerX-band Bruker E 500 (1997)
Magnetic Property Measurements SystemMPMS XL-7 Quantum Design (2011)
Dynamics τ~10-10 s Static τ~1 s
dc magnetization susceptibility study
0 50 100 150 200 250 30020x10-5
40x10-5
60x10-5
80x10-5
10x10-4
12x10-4
2 4 6 8 10 12 14 16 18 2080x10-5
90x10-5
10x10-4
11x10-4
[e
muO
e-1g
-1]
Temperature [K]
01 kOe 1 kOe 10 kOe 70 kOe
[e
muO
e-1g
-1]
Temperature [K]
0 40 80 120 160 200 240 2800
1
2
3
4
5 01 kOe 1 kOe 10 kOe 70 kOe
0 10 20 30 40 5008
10
12
14
16
18
1
[104
em
u-1O
eg
]
Temperature [K]
1
[104
emu
-1O
eg
]
Temperature [K]
dc magnetization reciprocal susceptibility
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
Sample preparation
025 050 075 100
025
050
075
100
025
050
075
100
mol
of CuO
mol
o
f V2
O 5
mol of Fe2O3
Fe2O3
CuO
V2O5
13 CuO + 5 V2O5 + 2 Fe2O3 rarr Cu13Fe4V10O44
A Blonska-Tabero J Therm Anal Calorim 110 (2012) 161
Structure ndash possible types
Lyonsite -Cu3Fe4(VO4)6 a new iron-copper vanadate mineral
six isolated VO4 tetrahedraFeO6 octahedra
square-planar CuO4 groups
HowardewansiteMineral NaCuFe2(VO4)3
In figure Mn3Fe4(VO4)6
VO4 FeO6 MnO5 MnO4 polyhedra
EPR and dc magnetometry
Magnetic resonance spectrometerX-band Bruker E 500 (1997)
Magnetic Property Measurements SystemMPMS XL-7 Quantum Design (2011)
Dynamics τ~10-10 s Static τ~1 s
dc magnetization susceptibility study
0 50 100 150 200 250 30020x10-5
40x10-5
60x10-5
80x10-5
10x10-4
12x10-4
2 4 6 8 10 12 14 16 18 2080x10-5
90x10-5
10x10-4
11x10-4
[e
muO
e-1g
-1]
Temperature [K]
01 kOe 1 kOe 10 kOe 70 kOe
[e
muO
e-1g
-1]
Temperature [K]
0 40 80 120 160 200 240 2800
1
2
3
4
5 01 kOe 1 kOe 10 kOe 70 kOe
0 10 20 30 40 5008
10
12
14
16
18
1
[104
em
u-1O
eg
]
Temperature [K]
1
[104
emu
-1O
eg
]
Temperature [K]
dc magnetization reciprocal susceptibility
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
Structure ndash possible types
Lyonsite -Cu3Fe4(VO4)6 a new iron-copper vanadate mineral
six isolated VO4 tetrahedraFeO6 octahedra
square-planar CuO4 groups
HowardewansiteMineral NaCuFe2(VO4)3
In figure Mn3Fe4(VO4)6
VO4 FeO6 MnO5 MnO4 polyhedra
EPR and dc magnetometry
Magnetic resonance spectrometerX-band Bruker E 500 (1997)
Magnetic Property Measurements SystemMPMS XL-7 Quantum Design (2011)
Dynamics τ~10-10 s Static τ~1 s
dc magnetization susceptibility study
0 50 100 150 200 250 30020x10-5
40x10-5
60x10-5
80x10-5
10x10-4
12x10-4
2 4 6 8 10 12 14 16 18 2080x10-5
90x10-5
10x10-4
11x10-4
[e
muO
e-1g
-1]
Temperature [K]
01 kOe 1 kOe 10 kOe 70 kOe
[e
muO
e-1g
-1]
Temperature [K]
0 40 80 120 160 200 240 2800
1
2
3
4
5 01 kOe 1 kOe 10 kOe 70 kOe
0 10 20 30 40 5008
10
12
14
16
18
1
[104
em
u-1O
eg
]
Temperature [K]
1
[104
emu
-1O
eg
]
Temperature [K]
dc magnetization reciprocal susceptibility
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
EPR and dc magnetometry
Magnetic resonance spectrometerX-band Bruker E 500 (1997)
Magnetic Property Measurements SystemMPMS XL-7 Quantum Design (2011)
Dynamics τ~10-10 s Static τ~1 s
dc magnetization susceptibility study
0 50 100 150 200 250 30020x10-5
40x10-5
60x10-5
80x10-5
10x10-4
12x10-4
2 4 6 8 10 12 14 16 18 2080x10-5
90x10-5
10x10-4
11x10-4
[e
muO
e-1g
-1]
Temperature [K]
01 kOe 1 kOe 10 kOe 70 kOe
[e
muO
e-1g
-1]
Temperature [K]
0 40 80 120 160 200 240 2800
1
2
3
4
5 01 kOe 1 kOe 10 kOe 70 kOe
0 10 20 30 40 5008
10
12
14
16
18
1
[104
em
u-1O
eg
]
Temperature [K]
1
[104
emu
-1O
eg
]
Temperature [K]
dc magnetization reciprocal susceptibility
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
dc magnetization susceptibility study
0 50 100 150 200 250 30020x10-5
40x10-5
60x10-5
80x10-5
10x10-4
12x10-4
2 4 6 8 10 12 14 16 18 2080x10-5
90x10-5
10x10-4
11x10-4
[e
muO
e-1g
-1]
Temperature [K]
01 kOe 1 kOe 10 kOe 70 kOe
[e
muO
e-1g
-1]
Temperature [K]
0 40 80 120 160 200 240 2800
1
2
3
4
5 01 kOe 1 kOe 10 kOe 70 kOe
0 10 20 30 40 5008
10
12
14
16
18
1
[104
em
u-1O
eg
]
Temperature [K]
1
[104
emu
-1O
eg
]
Temperature [K]
dc magnetization reciprocal susceptibility
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
0 40 80 120 160 200 240 2800
1
2
3
4
5 01 kOe 1 kOe 10 kOe 70 kOe
0 10 20 30 40 5008
10
12
14
16
18
1
[104
em
u-1O
eg
]
Temperature [K]
1
[104
emu
-1O
eg
]
Temperature [K]
dc magnetization reciprocal susceptibility
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
dc magnetization Curie-Weiss law
CWTT
CT
)(
Fe3+ 3d5 high-spin S=52 L=0 J=52 for g=2 μ=59 μB )1( JJgB
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
220 240 260 280 300
00
05
10
15
20
25
exp
-C
W [
10-6
em
u(g
Oe)
]
Temperature [K]
H=100 Oe
H=1 000 Oe
ZFC
H=10 000 Oe
dc magnetization high-temperature range
energynon-magnetic
magnetic
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
dc magnetization in an external field
0 10 20 30 40 50 60 70
00
02
04
06
08
00
05
10
15
20
25 10 20 30 40 50 60
Magnetic field [kOe]
250 K
200 K
Ma
gn
etiz
atio
n [ B
fu
]
2 K
5 K
HCHJg
kTkT
HJgJgHM H
B
B
coth)(
T [K] g JCH
[μBfumiddotOe]
2 115(2) 300(3)middot10-5
5 201(3) 200(5)middot10-5
200 9655(6) 0
250 9949(2) 0
Modified Langevin
AFM clusters
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
0 1 2 3 4 5 6 7 8 9
-4
-3
-2
-1
0
1
2
3
4
EP
R a
mpl
itude
[arb
uni
ts]
Magnetic field B [kG]
290 K260 K
230 K
4 K
170 K
70 K
40 K
255 K148 K
EPR spectra and fitting
0 1 2 3 4 5 6 7 8-15
-10
-5
0
5
10
EP
R a
mpl
itude
[ar
b u
nits
]Magnetic field B [kG]
T=305 K
220)(BBB
BABA
r
Lorentzian lineshape
Br - resonance fieldΔB -linewidth
20int BAI
Iint ndash integrated intensity
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
0 50 100 150 200 250 300195
200
205
210
215
220
225
g-fa
ctor
Temperature [K]
EPR g-factor
rBBgh
0 50 100 150 200 250 300
3000
3050
3100
3150
3200
3250
3300
3350
3400
Res
onan
ce f
ield
[G
]
Temperature [K]
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
0 50 100 150 200 250 30006
08
10
12
14
16
18
20
22
24
26
Line
wid
th [
kG]
Temperature [K]
nEPRNTTCBTB
10)(
EPR linewidth
000 002 004 006 008 01070
75
80
85
90
Ln(
H [
G])
Temperature-1 [1K]
12 K
60 K
)5(880
)5(72
n
KT EPRN
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
3335 3340 3345 3350146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
300 305 310 315 320 325 330 335 34010
15
20
25
30
35
40
45
50
Line
wid
th [k
G]
Resonance field [kG]
290K
280K
270K
260K
250K
240K
230K220K
190K 180K
170K160K
150K
140K
130K
120K
110 K
Line
wid
th [
kG]
Resonance field [kG]
8 K 10 K
122 K
148 K
173 K
199 K
255 K305K
EPR linewidth vs resonance field
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
0 50 100 150 200 250 30015
20
25
30
35
40
45
50
EP
R in
tegr
ated
inte
nsity
[ar
b u
nits
]
Temperature [K]0 50 100 150 200 250 300
0
1
2
3
4
5
6
7
EPR
arb
un
its
Temperature [K]
I0=53731010 C2=1131012
TCW=-602 K
CWTT
CITI
2
0int )(
EPR integrated intensity
140 160 180 200 220 240 260 280 30000
02
04
06
08
10
12
14
Inte
grat
ed in
tens
ity [
arb
uni
ts]
Temperature [K]
AFM clusters
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
General picture of the magnetic state of Cu13Fe4V10O44
0 50 100 150 200 250 300Temperature [K]
PARAMAGNETICAFM
TN=27 K
C-W STATEAFM CLUSTERS
CLUSTERS
ISING CHAINSAFM PHASE SEEDS
THE END
Thank you
THE END
Thank you
