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· Theory supported by graphical explanations

esto es lo que vimos con Mailen

· Vectorial model becomes useless….

→ but still more understandable

· A lot of supplementary subjects to go through

Se basa en producto de operadores

Expertise knowledge on NMR involves:

- Product operators
- Gradients
- Coherence transference pathways

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 Product Operators

NMR is almost all

rotations.

Notice that the

coordinate system
1 x y satisfies the “right

M x = 0
hand rule”. If you
y point your right
thumb along the z-
0 z x
axis, you fingers will
z close from x to y.

0  x

M y = 1 y
y
0 z
z
x
0 x

M z = 0 y
y
1 z

x
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 Rotation Matrices

1 0 0 
Rx ( ) = 0 Cos( ) − Sin( )
 
0 Sin( ) Cos( ) 
3D rotation matrices. They
rotate the vector around the
axis that defines the vector.

Cos( ) 0 − Sin( )
Ry ( ) =  0 1 0 
 
 Sin( ) 0 Cos( ) 

Cos( ) − Sin( ) 0
Rz ( ) =  Sin( ) Cos( ) 0
 
 0 0 1

interaccion entre una matriz y un

Rotation vector de rotación

1 0 0  0
Rx ( ) = 0 Cos( ) − Sin( ) Mz = 0
   
0 Sin( ) Cos( )  1

Here is an example of a rotation of Mz around the x-axis by an angle :

1 0 0  0  0 + 0 + 0   0 
0 Cos( ) − Sin( ) 0 =  0 + 0 − Sin( )  = − Sin( )
      
0 Sin( ) Cos( )  1 0 + 0 + Cos( )  Cos( ) 

Notice that if =0, the vector stays the same. If

=p/2, the vector is rotated to the –y axis.
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 General Rule of Rotations
Every rotation in 3D space leads to 2 terms. The first term is pointing in
the same direction and is multiplied by Cos() where  is the rotation
angle. The second term is along the axis that the vector is rotated into
and is multiplied by Sin().

1 0 0  0  0 + 0 + 0   0 
0 Cos( ) − Sin( ) 0 =  0 + 0 − Sin( )  = − Sin( )
      
0 Sin( ) Cos( )  1 0 + 0 + Cos( )  Cos( ) 

For example, in the rotation above, a rotation of  around the x-axis

(because it is the Rx rotation matrix) of Mz produces Mz*Cos()-
My*Sin().

Product Operators are a mathematical shorthand to

do rotations.
For example, the rotation we just saw:

1 0 0  0  0 + 0 + 0   0 
0 Cos( ) − Sin( ) 0 =  0 + 0 − Sin( )  = − Sin( )
      
0 Sin( ) Cos( )  1 0 + 0 + Cos( )  Cos( ) 
becomes: vector que interacciona
con el

Ix
operador lleva el sombrerito

Iz ⎯⎯⎯⎯→ Iz cos() − I y sin()

vector de magnetizacion
Z da como resultado estos vectores

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 Examples of pulses

Ix
Iz ⎯⎯⎯⎯→ Iz cos() − I y sin()

0Ix
Iz ⎯ ⎯⎯⎯⎯→ −I y 45Î
I z ⎯⎯ ⎯ x → I cos(45) − I sin(45)
180Ix
z y

Iz ⎯ ⎯⎯⎯⎯⎯→ −Iz 1 1
= Iz − Iy
0Iy 2 2
Iz ⎯ ⎯⎯⎯⎯→ I x
−0Iy
Iz ⎯ ⎯⎯⎯⎯⎯→ -I x
0Ix
I x ⎯ ⎯⎯⎯⎯→ I x

Chemical shift! The chemical shift operator works exactly like

a pulse operator, but it only acts along the z-axis.

ItIz
I x ⎯ ⎯⎯⎯⎯→ I x cos(t) + I y sin(t)
ItIz
I y ⎯ ⎯⎯⎯⎯→ I y cos(t) − I x sin(t)

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 1D NMR experiment
90x

a
a b c

90Î  tIˆ (+ relaxation)

I z ⎯⎯⎯ x → −I ⎯⎯I⎯⎯ z → −I cos( t ) + I sin( t )
y y I x I

a b c
Scalar (J) Coupling

These states each form a 4x4 matrix that is the direct product
of the two corresponding 2x2 matrices. For example:

1 1 0  1 1 0 
Iz = Sz =
2 0 − 1
No coupling
2 0 − 1

1 1 0  1 1 0 
I z Sz =  
2 0 − 1 2 0 − 1
 

1 0 0 0 Coupling
 − 1 0 0
1 0
=
4 0 0 − 1 0
  11
0 0 0 1