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• The nuclei of many atoms have a property called nuclear spin (I)
N N
S Magnetic
Magnetic
Field N Field
S S
Spin I=1/2
S
I=1/2, Why two orientations?
A particle with spin I=1/2 has two components +1/2 and -1/2.
We can picture this as being clockwise (+1/2) rotation or
anticlockwise (-1/2) rotation.
We refer to the two states as alpha, , and beta, , (just like
electrons which also have a spin of 1/2).
In an external field one lines up with the field and one against
+1/2
Magnetic
Field
-1/2
Is it always two orientations? NO
I = 1/2 I=1
Magnetic Field Magnetic Field
+1
+1/2
-1/2
-1
Larmor precession
The spin axis will rotate around the direction of the field (like
the gyroscope under gravity). The angle is always the same.
b state
Energy
a state
∆E = B0 h/2π
2. Of these 12C and 16O have spin I=0 and hence no NMR
absorption.
3. 1H has spin I=1/2 and 14N has I=1 - so both have NMR
absorption (but in different spectral regions).
4. 2H with spin I=1 and 13C has I=1/2 are also used sometimes.
Not to scale:
Magnets are large and
sample tube small
If this was the whole story there would only be a single line in the
spectrum telling us there was hydrogen in a compound - hardly any
use at all! BUT…
NMR spectrum of
3,5-dimethylbenzoic acid
Many groups shield the nucleus but some can actually increase
the field. These are said to deshield the nucleus.
Bdesh
Beff
B0
Chemical shift and the delta scale, d
The actual absorption frequencies depend on the magnet used in
the apparatus, making it difficult to compare spectra from
different machines. So the delta scale, is used instead.
d = n n- n ref 10 6 ppm
ref
The scale is normally given in parts per million, ppm, since the
shifts are very tiny.
d scale reference - tetramethylsilane, TMS
Because of molecular symmetry all
12 protons of TMS absorb at the same
frequency giving a strong single peak.
1,2-dichloroethane:
Four chemically equivalent
hydrogens. So one peak at
d=3.73 - shifted by the
presence of a single
adjacent Cl atom.
1,1-dichloroethane:
Three chemically equivalent
hydrogens in CH3 and a
single H atom. So expect
two peaks at d=2.06 and
d=5.89 - shifted by the
presence of two adjacent Cl
atoms.
Why the extra lines?
Spin-Spin coupling
The expected peaks have been split into a doublet at d=2.06 and a
quartet at d=5.89. Such spin-splittings are frequently observed at
high resolution.
1H 1H 1H 1H
A B A B
Bo Bo
HA is shielded - HA is deshielded -
moves to lower freq moves to higher freq
Spin-spin coupling mechanism
1H without 1H
A B
J
1H is
B 1H is
B
The NMR spectrum now sees two lines of 50% intensity instead
of 1 line at 100% intensity. This is called spin-spin splitting
Spin-spin coupling mechanism
1,1-dichloroethane:
Three chemically equivalent
hydrogens in CH3 see a single
H atom. In 50% of molecules
it is and in 50% . So the
peak at d =2.06 splits into two
half-intensity lines.
Net deshielding
2 and 1 3/8
3/8
1 and 2
Net shielding
3 1/8
Spin-spin coupling mechanism
1H without CH3
J J J 1H with CH3
3 2, 1 1, 2 3
d
N Multiplet Intensities
0
1
2
3
4
5
6
ppm
15 10 7 5 2 0
TMS
ppm
z z
M
x x
y y
Bo Bo
Pulsed Fourier Transform NMR Spectroscopy
Bo
M rotates
towards xy Circularly polarised magnetic
plane x field B1 in the x direction.
y
Bo Detector coil
z
M
Bo
M
x
y
M rotates in xy plane. Every
The B1 pulse is applied time it passes the detector
long enough to rotate M coil it generates a current
into the xy plane
Free induction decay - several spins
B0 Detector coil
FID
NMR Spectrum
2D NMR