Tema Nro. 3.

MASNMR, NQR & EPR

NMR & MAS NMR

Nature of Nuclear Magnetic Resonance (NMR) Spectroscopy
• Electrons, protons, and neutrons have spin
• Overall spin (I) of nucleus determined by numbers of
neutrons and protons:
1. Number of of neutrons and number of protons are even, then nucleus has spin
of 0.
2. Number of neutrons plus number of protons are odd, then nucleus has spin of
half integer (1/2, etc).
3. Number of neutrons and number of protons are odd, then nucleus has spin of
whole integer (1, 2, etc.)

Examples of spin 1/2 nuclei: 1H, 13C,15N, 19F, 31P

 Splitting of Energy Levels
Nucleus of spin I has 2I+1 possible orientations
Spin 1/2 has 2 possible orientations

When magnetic field is applied, the energy levels split

orient with () or against () the magnetic field
Which orientation will be lower energy?
Aligning with () the magnetic field
hB0 No field Applied field
E =
2
 = gyromagnetic ratio
E
B0=magnetic field
 Populations of energy levels
The Boltzmann distribution describes the relative populations
of energy levels at a given temperature
p e E 
Ratio of populations:   E 
p e
p
Simplify expression:  e E  e  E   e  (E  E  )  e E
p
 p 
E

Plug in for :  e kT
p

Calculate relative populations of energy levels at room temperature.
T = 300 K B0 = 21 T  = 27x107 radT-1s-1
 x 10-25 J = 0.36 J / mol
E = 6.0

This corresponds to a population ratio of 0.99986

 NMR Experiment
• Apply radiowaves at same frequency as difference
in energy levels
• Causes some spins to go to higher energy state
– Called a spin flip
• Turn off radiowaves, spins will return to equilibrium
– Relax back to lower energy level

time
+RF pulse
 The spectral region excitation
E = 6.0 x 10-25 J = h
 = E / h = (6.0 x 10-25 J / 6.626 x 10-34 Js)
 = 9.0 x 108 Hz = 900 MHz

time

This induces a voltage in the detection coil around the sample:

free induction decay (FID)
 The NMR Experiment

Can write the FID as

f (t)  (cos 0 t  isin  0 t)et /T2  e(i 0 1/T2 )t

To get the NMR spectrum, perform a Fourier

transform:

F( )   f (t)e it
dt

 The NMR Experiment
Every frequency component in the FID yields a line in the absorption
spectrum at the precession frequency:
 The NMR Experiment
Electron density around nucleus reduces resonance frequency of the nuclear spin: shielding
B B(1  ) B
Frequency given by:   
2 2 2

 depends on electron density around nucleus; changes depending on neighbors

Leads to shift in frequency
 shifts are dependent on chemical environment
Chemical
Chemical Applications of NMR

=>
 Larmor frequency
B0, z

M L   B0 L  B0
2
y For the magnetic field of 11.744 Tesla
we obtain for L about
500 MHz for 1H,

x 126 MHz for 13C

L 130 MHz for 27Al
202 MHz for 31P
77 MHz for 2H
For Nuclei with I > ½ the Presence of a
Quadrupolar Interaction must be Considered

This leads to broadening for the recorded peaks

(unresolved signals), which explains why the most
popular applications of NMR correspond to nuclei
with I = ½ (1H, 13C, 19F, 27Al, 29Si, 31P, ….)

For Nuclei with I >1/2 the energy levels could be resolved in absence
of applied field. The related spectroscopic technique is known as
Nuclear Quadrupole Resonance (NQR)
NMR spectra (1H) are usually recorded in Deuterated solvents.

The characteristic time of NMR is about 10-7 sec. The NMR

experiment is detecting the average for all the anisotropic
intermolecular interactions within the solvent. This explains
that for molecules of small and medium size the recorded
spectra are formed by narrow lines.
For a viscous material or a solid the spectum is formed by
broad and overlapped peaks and it reveals the local
anisotropy around the sensed nucleus.
 How does it effect the NMR spectrum
• Each molecular orientation gives rise to a
difference resonance frequency

• In powder we have the sum of all distributions

• In the liquid state these anisotropic properties
are averaged on the NMR timescale 13
Which interactions in NMR
Isotropic Anisotropic

H  H CS

H  H CS  H J  H CSA

H  H CS  H J

H  H CS  H J  H CSA  H Dipolar
H  H CS  H J  H CSA  H Dipolar  H Q 14
Describing interactions: tensors
We are concerned with 3 types of tensors
• Zero rank tensors
– Physical property independent of coordinate system
in which it is described (scalar, distance)
• First rank tensors
– Coordinate, depends on frame of reference (vector,
has size and direction)
• Second rank tensors
– Multiple first rank tensors e.g. stress (matrix)
• Higher rank exist – but we will not be considering

15
 Describing interactions: tensors
Rank zero tensor Rank one tensor

B0

Isotropic chemical shift,

J-coupling (0,0,Bz)

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 Describing interactions: tensors
• Second rank tensors
k

i j k

  xx  xy  xz 
 
i     yx  yy  yz 
   
j  zx zy zz 

zz

  xx 0 0 
yy
 
 PAS   0  yy 0 
xx y
 0 
 0  zz 
x

17
 Parameterizing 2 rank tensors nd

• In cartesian notation tensors defined by principle

components, Axx, Ayy and Azz
• Frequently parameterized with a  Tr  A  A  A  A xx yy zz

a
  Azz 
3
Ayy  Axx


a a a
Azz   Axx   Ayy 
• This assumes 3 3 3

• Thus the asymmetry 0.0<<1.0 and anisotropy can

be both positive and negative
18
 Chemical Shielding Anisotropy
• Perturbation of the magnetic field due to
interaction with surrounding electrons

• Inherently asymmetric (e.g. electron

distribution surrounding carbonyl group)
19
 Dipolar Interaction
Classical interpretation Quantum mechanical
B0
 0  1 2  ˆ ˆ 3  ˆ   ˆ   
HD   I1 I 2  2  I1.r12  I 2 .r12  
2 4 r12  3
r12   
  
 Iˆ1 DIˆ2
1 where:

1 0 0 
    
Classical interaction energy between two D  0 1 32  0 1 0 
4 r12  
0 0  2
magnetic (dipole) moments when both
are aligned with the magnetic field:
• Symmetric second rank axially symmetric
0 1 tensor.
E  
1 2 (1  3 cos 2
) • Again we need to rotate from the PAS to
4 r12
3
LF to obtain resonance frequency.

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 Orientation dependence of dipolar
interaction
Homo-nuclear Dipolar Hamiltonian: Hetero-nuclear Dipolar Hamiltonian:

0  1 2  (1  3 cos2  )  ˆ ˆ  ˆ ˆ  
H D , II 
4 r123 2
 3 I1 z I 2 z   I 1 I 2  
   H D , IS 
4 r123 2

 0  1 2 (1  3 cos 2  ) ˆ ˆ
2 I1 z I 2 z 

dip dip

dip=20 kHz 21
 Magic Angle Spinning
Seeks to reintroduce averaging process through
mechanical rotation

Sample rotors (Varian)

Magic Angle Spinning Probehead (Doty)

22
Averaging of anisotropic interactions

23
 29
Si MAS NMR spectrum of silicalite-1

SiO2 framework consisting of 24 crystallographic different silicon sites per unit cell (Fyfe 1987).
 29
Si MAS NMR
Q0
Q1 alkali and
alkaline earth
Q2 silicates
Q3
Q4

Q3 Si(3Si, 1OH)

Si(4 Al)
Si(3 Al)
aluminosilicate-
4
Q type zeolites
Si(2 Al)
Si(1 Al)
Si(0 Al)

Si(2 Zn zincosilicate-type zeolites

Q4 ) VP-7, VPI-9
Si(1 Zn
)
60 70 80 90 100 110 120 130
ppm
 27
Al MAS NMR
coordinated
aluminophosphates
6-fold

aluminoborates
aluminates
aluminosilicates
aluminophosphates
coordinated

aluminoborates
5-fold

aluminates
aluminosilicates
aluminophosphates
coord. coordinated

aluminoborates
4-fold

aluminates
aluminosilicates
3-fold

aluminosilicates

120 110 100 90 80 70 60 50 40 30 20 10 0 10 20

ppm
 Al MAS NMR spectra
27

of a hydrothermally treated zeolite ZSM-5

four-fold five-fold six-fold
coordinated coordinated coordinated

L = 195 MHz
Rot = 15 kHz

L = 130 MHz
Rot = 10 kHz

100 80 60 40 20 0 20 40 60

 / ppm
Take-away message:
A signal narrowing by MQMAS or DOR is not possible, if the line broadening is
dominated by distributions of the chemical shifts which are caused by short-range-order
distortions of the zeolite framework.
 129
Xe MAS NMR Zn3[M(CN)6]2
Cd3[M(CN)6]2

Xe
NQR: NMR without applied magnetic field

I 1 I=3/2
rf pulse
m  3 / 2
h Q
m  1 / 2
nucleus Electric field gradient (EFG)

e 2 qQ 2 eq  Vzz
Resonance frequency Q  1   Vxx  V yy  Vzz
2 3
 14
N NQR
For the spin 1 14N nuclei energy levels and allowed transitions are:

3e qQ   
2 3e 2 qQ    e 2qQ
    1   0  
1   4h  3  2h
4h  3 

Q is the nuclear electric quadrupole moment, q the maximal component of EFG

tensor  is the asymmetry parameter.
 Detection process

Before stimulation

RF field is applied After excitation is removed

NQR Land Mines Detection
 Other Applications

Airport Security
The same technology used in nuclear LMD can also
be used to scan luggage in airports
This technology will allow faster and far
more accurate scanning of luggage
 EPR (ESR)
Electron Paramagnetic Resonance (EPR)
or
Electron Spin Resonance (ESR)


Ms = +1/2
E = g b B

  where the g-value

gives characteristic info.
No magnetic field  E is microwave region
B=0 Ms = -1/2,
antiparallel to B more stable
Magnetic field
B≠0
En que casos se puede obtener un espectro EPR ?

-Radicales libres, en estado sólido, líquido o gaseoso.

-La mayoría de los iones de transición y tierras raras.
-Defectos en los cristales iónicos.
-Electrones de conducción en los semiconductores.
-Biradicales, sistemas en estado triplete, etc.
Áreas de Aplicaciones de EPR

- Procesos redox
- Cinéticas de reacción
- Reacciones poliméricas
- Reacciones enzimáticas
- Fotosíntesis
- Radicales en tejidos vivos
- Fenómenos de relajación
- Transiciones de Fase
- Semiconductores
- Materiales Magnéticos
- Geocronología
- etc.
 Algunos Conceptos Iniciales
s= - ge BS E= - . B H = ge BS.B H = ge BSz Bo

H = H0 + H1 + H2 H1 = ge BB · S H2 = BB · L + L · S

Ej. EPR: Bo = 0.32mT  9.5 GHz (32 mm): MW

RMN: 8.46T  360MHz

 Proceso de relajación

(1/T1) = W + W: Espín - Red

Recordemos que: Et h

El ancho de las líneas podemos controlarlo mediante el
campo aplicado y la frecuencia de irradiación

El campo local que experimentara un electrón dado esta afectando

por la fluctuación en los electrones y de su correspondientes espines.
Esto da lugar a un segundo tiempo de relajación (espín-espín): T2

f(w) = {(1/)(1/T2)}/{(1/T2)2 + (o - )2}

Interpreting EPR.1
The Derivative Signal
A Free Electron in a Magnetic Field

+½: E = +½geβB0

ΔE = geβB0

-½: E = -½geβB0

β: Bohr magenton
B0: magnetic field
ge: g value

For a free electron:

g = ge = 2.00232

40
 Proportionality Factor
• Measured from the center
of the signal
• For a free electron
– 2.00232
• For organic radicals
– Typically close to free-
electron value
– 1.99-2.01
• For transition metal compounds
– Large variations due to spin-orbit coupling and
zero-field splitting
– 1.4-3.0

41
Resonance Measurement

EPR spectrometer is:

•constant frequency
o X-band: 9-10 Giga Hertz (GHz)
o Q-band (high field): 35 GHz
• vary B field (~3500 Gauss)
to bring into resonance;
• E is absorbed by the sample
when the frequency of the radiation
is appropriate to the energy
difference between two states of the
electrons in the sample

(10,000 Gauss = 1 Tesla)

Spin-orbit Coupling

Resonance condition: ΔE = hν = geβB0

When the electron is bound to one, or more nuclei, then a virtual observer on the
electron would experience the nucleus (nuclei) as an orbiting positive charge producing a
second magnetic field, δB, at the electron.
hν = geβ(Be + δB)
Since only the spectrometer value of B is known:
hν = (ge + δg)βB = gβB
The quantity ge + δg contains the chemical information on the nature of the bond
between the electron and the molecule, the electronic structure of the molecule.

43
Line Shape of EPR Spectra

44
Spin-orbit Coupling

Example: compound with axial paramagnetic

anisotropy.
This will have a different g value for different
orientations dependent on the alignment of B
along the z axis or the y or x axes.

45
 Interacciones hiperfinas
Tienen su origen entre la interacción entre el espín del electrón
y el espín nuclear. Da origen a desdoblamientos Zeeman

Interación de contacto de Fermi: aiso = (8/3)gegNeN|(0)|2

Si hay n núcleos vecinos de espín I
interactuando con el electrón entonces
encontraremos 2nI + 1 transiciones.

El conocimiento del número y separación

de una estructura hiperfina conduce al
número y la naturaleza de los núcleos
interactuantes
Hyperfine Interactions

Interactions of the electron spin with the nuclear spin of the metal ion nucleus or first
coordinate sphere ligands nuclei or other electron spins within 10 Ǻ distance cause
additional splitting.

47
Hyperfine Interactions

48
Type Identification - Metals

Cu2+, d9,  = 3/2

Mn2+, d7, I = 5/2

(S = 5/2)

49
Relative Intensities for I = ½

50
 Relative Intensities for I = 1
N Relative Intensities
0 1
1 1:1:1
2 1:2:3:2:1
3 1:3:6:7:6:3:1
4 1 : 4 : 10 : 16 : 19 : 16 : 10 : 4 : 1
5 1 : 5 : 15 : 20 : 45 : 51 : 45 : 20 : 15 : 5 : 1
6 1 : 6 : 21 : 40 : 80 : 116 : 141 : 116 : 80 : 40 : 21 : 6 :
1
51
Relative Intensities for I = 1

52
 Hyperfine Interactions

EPR spectrum of benzene radical anion

53
 Interacciones Hiperfinas Anistrópicas
Los acoplamientos hiperfinos anisotrópicos son debidos a la interacción dipolar entre los
momentos magnéticos nuclear y electrónicos cuando el electrón desapareado no está en
orbitales de simetría esférica ( orbitales p, d, f). El acoplamiento surge de la interacción
Dipolar clásica entre los momentos magnéticos cuya energía viene dada por:

E = S.N/r3 – 3(S.r) (N.r)/r5

Ej.: S = ½; I = 3/2
 Estructura Fina
Se presenta en aquellos sistemas en los que están presentes dos o más electrones
desapareados, de forma que el espín total es mayor que 1/2.

Ej. Cr3+ en un campo cubico

Una distorsión axial hace

que se separen los niveles
MJ= ±3/2 y MJ= ±1/2
Type Identification – Iron-sulfur Clusters
[2Fe-2S]1+ S = ½
[2Fe-2S]2+ S = 0
20-70 K

[3Fe-4S]0 S = 2
4-10 K
[3Fe-4S]1+ S = ½

4-20 K
[4Fe-4S]1+ S = ½
[4Fe-4S]2+ S = 0 4-10 K

(HiPIP)
[4Fe-4S]2+ S = 0
[4Fe-4S]3+ S = ½

56