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1
Molecular nanomagnets as milestones for the study of low-dimensional
magnetism: fundamental physics and applications
Wide-band solid-state NMR at a glance
Molecular spin dynamics vs temperature
Low temperature quantum level crossing
2
3
Possible applications of MNMs :
High density magnetic memory
Magneto- optical recording
Quantum computing
Spintronics
Magnetic sensorsβ¦
4
As all molecular clusters, studying bulk means
studying single molecule as Jinter-mol << Jintra-mol
As all molecular clusters, finite number of ions :
accurate spin Hamiltonian and exact
calculation of energy levels and eigenfunctions
π»=π½
ππ . ππ+1 +
π
π ππ +
π
πππ ππ . ππ + πππ΅ π΅
π>π
ππ
π
Highly symmetric geometry
5
Ideal physical framework for low dimensional
magnetism ( 0-D and/or 1-D)
πππ+ S=0
Finite size system
Reduced number of spins
Discrete energy levels structure
Quantum phenomena
πͺππ+ , S=3/2
οΌ Spin topology of a Quasi-Zero-Dimensional magnetic system......
οΌ βOpenβ molecular ring : peculiar spin dynamics
οΌ Interesting quantum behaviors due to βrealβ or anti- level crossing
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By NMR
we are measuring the response of nuclei but, through it, we are studying
the physical properties of the whole system (electrons, nuclei & phonons)
How is it possible
Nuclei ?
π»ππ
Nuclei are a local probe
But
in interaction with the whole system
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electron
π»ππ
phonon
Advanced tools for molecular spin dynamics investigation
οΌ 1H NMR
53Cr
NMR
F NMR
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53Cr
NMR
οΌ 1H NMR
F NMR
19
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Abundance proton
(High sensitivity )
Study of NMR relaxation rates
and spectra
5000
NMR Spectrum
4000
I(a.u.)
3000
Full width at half maximum
(FWHM)
From 1H NMR spectrum it is possible to extract the
Full Width at Half Maximum β FWHM, given by :
2000
< βπ 2 >π +< βπ 2 >π
πΉππ»π β
1000
0
-1.5
-1.0
-0.5
0.0
w(MHz)
0.5
1.0
120
1.5
300
H=1.5T
H=0.5T
H=0.3T
80
FWHM(kHz)
200
FWHM(kHz)
Hο C
πͺππ ππ
250
Cr8Zn
150
Cr8
60
40
20
0
100
50
0
1
0.47 T
1.23 T
πͺππ
100
10
100
1
10
T(k)
100
Paramagnetic behaviour of πΆπ8 ππ
in the high temperature region (T>20K)
T(k)
ο The temperature and magnetic field dependence of 1H FWHM is similar to
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other antiferromagnetic molecular rings, but
β¦β¦.
300
Hο C
Dramatic
Increase!!!
250
H=1.5T
H=0.5T
H=0.3T
FWHM(kHz)
200
Cr8Zn
150
At relatively high fields, the gap is reduced
and πΊπ» =0 and πΊπ» = 1 states
are populated equally
100
50
π΅πππ‘π§ππππ ππ’ππ ;
π΅πΊπ»=π = π΅πΊπ»=π πββπ¬/ππ©π»
8
0
1
10
100
6
Energy(cm)-1
T(k)
2
For T<20K, condensation in the G.S.
0
πΉππ»π β
10
π―πππππ = π―π
4
First excited state
First
state M
ST=1=+1
ST=1,
s
οο
οΌοΌ
2 > 1 1.5T
< βπ 2 >π +< βπ
0
π
Ground state ST=0
2
3
4
Magnetic field (T)
5
6
Cr8 0.47 T
Cr8 0.73 T
Cr8 1.23 T
Fe6(Na) 0.5 T
Fe6(Na) 1 T
Fe6(Li) 1.5 T
Fe10 1.28 T
Fe10 2.5 T
1.0
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πͺππ ππ
8
R/Rmax
πͺππ , πππ , ππππ β¦
Cr8Zn ( HοC)
H=1.5T
H=0.5T
H=0.3T
7
0.8
0.6
0.4
0.2
0.0
0.1
1
10
T/T0(H)
Homometallic rings (previous studies):
5
-1
T1 (ms)
6
4
πΉ π―, π» =
3
π
ππ π»
=π¨ π
π»π ππ»
ππ π» + ππ
2
Two alternatives;
0
25
50
75
T(k)
Current case (heterometallic Cr8Zn):
π
πΉ π―, π» =
π»π ππ»
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π
ππ π» β = πͺπ»πΆ
ππ
ππ π» =
πππ ,
π
π
ππ π»
= π¨β² π
π»π
ππ π» + ππ Theoretical calculation in progressβ¦
πππ β πββ/π»
ο At low T (much less than the gap among ππ =0 and ππ =1, e.g. T=1.7K)
molecular rings populate the ground state
ο The local (at 1π» sites) magnetic field due to the contribution of electronic
(molecular) magnetic moments, becomes:
π―πππππ = π―π + π―ππππππ
πΉππ»π β
< βπ 2 >π +< βπ 2 >π
approx. ο΅ M
< βπ 2 >π =
1
π
πΎ2
=
π
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π
( πβπ
A(ππ,π )
[
π
2
< ππ
,π β π0 >βπ‘ )
πβπ
πβπ
ππ,π 3
< ππ§,π >βπ‘ ]2
οΌ NMR spectral broadening due to the increase
of the electronic magnetization value
Cr8Zn M(H) a 2K
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parall
perpen
4
2
ο³ [emu/g]
non-magnetic
Ground State ST = 0
0
-2
-4
-6
-5
-4
-3
-2
-1
0
ο0H [Oe]
magnetic
Ground State ST = 1
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Calculated energy levels in
external magnetic field
1
2
3
4
5
4
x 10
M(H) curve at T=2K
magnetic
Ground State ST = 2
12000
Cr8Zn NMR Spectrum
H=1.8T
Larmor Frequency=76.576 MHz
10000
Proton NMR spectra versus magnetic field on πͺππππ based
on energy levels structure by using frequency sweep technique
at the fixed temperature (T=1.7 K)
6000
4000
2000
0
-0.5
0.0
ο·ο¨οο
z)
πβπ
π (π΄π―π)
0.5
NMR spectra before the first level crossing
(ππ = 0 β Non-magnetized system)
οΌ NMR spectra broadening by
passing of crossing level
H=3T
1.0
Larmor Frequency=127.688MHz
15000
10000
5000
5000
Cr8Zn NMR Spectrum
H=7.5T
4000
Larmor Frequency=319.214MHz
0
-1.0
-0.5
0.0 ο·ο¨οοz)
π β ππ (π΄π―π)
0.5
1.0
3000
1H
NMR spectra after the first level crossing
(ππ = 0 β ππ = 1)
( Non-magnetized »»» Magnetized system)
I(a.u.)
1H
Cr8Zn NMR Spectrum
20000
-1.0
I(a.u.)
I(a.u.)
8000
2000
1000
0
-1.0
Calculated energy levels in
an external magnetic field
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-0.5
0.0
0.5
1.0
πο·ο¨οο
β πz)π (π΄π―π)
1H
NMR spectra after the second level crossing
(ST = 1 ο ST = 2)
Future investigation:
spin-lattice relaxation rate study of spin dynamics
(also level crossing problem details and mix of eigenfunctions)
Anti level crossing; Mixed functions
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Real level crossing; Unmixed functions
Conclusions:
ο Temperature spin dynamics of πͺππ ππ detected by β 1H NMR 1/π»π β is qualitatively
similar to homometallic rings; an exact calculation of correlation function is needed.
At low temperature 1H NMR spectra broadening reflects the effects of M increase
when Quantum level crossing occur
ο
Future issues :
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ο
Theoretical investigation of spin dynamics vs temperature
ο
Quantum effects due to βReal β/ Anti level crossing studied by means of
low-T 1H NMR spin-lattice relaxation rate
January 15th 2013
Italy
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T2 relaxation curve
T1 relaxation curve
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NMR spectrum