NMR Spectroscopy
Where is it?
1nm 10 102 103 104 105 106 107
(the wave) X-ray UV/VIS Infrared Microwave Radio
Frequency
(the transition) electronic Vibration Rotation Nuclear
(spectrometer) X-ray UV/VIS Infrared/Raman NMR
Fluorescence
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Before using NMR
What are N, M, and R ?
Properties of the Nucleus
Nuclear spin
Nuclear magnetic moments
The Nucleus in a Magnetic Field
Precession and the Larmor frequency
Nuclear Zeeman effect & Boltzmann distribution
When the Nucleus Meet the right Magnet and radio wave
Nuclear Magnetic Resonance
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Properties of the Nucleus
Nuclear spin
Nuclear spin is the total nuclear angular momentum quantum number. This
is characterized by a quantum number I, which may be integral, half-integral
or 0.
Only nuclei with spin number I 0 can absorb/emit electromagnetic
radiation. The magnetic quantum number mI has values of –I, -I+1, …..+I .
( e.g. for I=3/2, mI=-3/2, -1/2, 1/2, 3/2 )
1. A nucleus with an even mass A and even charge Z nuclear spin I is zero
Example: 12C, 16O, 32S No NMR signal
2. A nucleus with an even mass A and odd charge Z integer value I
Example: 2H, 10B, 14N NMR detectable
3. A nucleus with odd mass A I=n/2, where n is an odd integer
Example: 1H, 13C, 15N, 31P NMR detectable
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Nuclear magnetic moments
Magnetic moment is another important parameter for a nuclei
= I (h/2)
I: spin number; h: Plank constant;
: gyromagnetic ratio (property of a nuclei)
1H: I=1/2 , = 267.512 *106 rad T-1S-1
13C: I=1/2 , = 67.264*106
15N: I=1/2 , = 27.107*106
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AT 71000 GAUSS (7.1 TELSLA)
(1T = 10,000 G)
W 0 (MHz) 0 30 75 121 280 300 320
15 13 31 19 1 3
Nucleus N C P F H H
Nuclei of Major Interest to NMR Spectroscopists
Abundance At
Iostope Ζ Spin μ2 γ ×10-8 b
(%) 7.04 T
1
H 99.9844 1 1/2 2.7927 2.6752 300
2
H 0.0156 1 1 0.8574 0.4107 46
13
C 1.108 6 1/2 0.7022 0.6726 75.4
14
N 99.635 7 1 0.4036 0.1933
15
N 0.365 7 1/2 -0.2830 -0.2711 30.4
19
F 100 9 1/2 2.6273 2.5167 282.3
31
P 100 15 1/2 1.1305 1.0829 121.4
a Magnetic moment in units of the nuclear magneton, eh/(ΔμMp c)
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b Magnetogyric ratio in SI units
The Nucleus in a Magnetic Field
Precession and the Larmor frequency
• The magnetic moment of a spinning nucleus processes with a characteristic
angular frequency called the Larmor frequency w, which is a function of r and B0
Remember = I (h/2) ? J
Angular momentum dJ/dt= x B0
Larmor frequency w=rB0
Linear precession frequency v=w/2= rB0/2
Example: At what field strength do 1H process at a frequency of 600.13 MHz? What would be the
process frequency for 13C at the same field?
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Nuclear Zeeman effect
• Zeeman effect: when an atom is placed in an external magnetic field, the
energy levels of the atom are split into several states.
• The energy of a give spin sate (Ei) is directly proportional to the value of mI
and the magnetic field strength B0
Spin State Energy EI=- . B0 =-mIB0 r(h/2p)
• Notice that, the difference in energy will always be an integer multiple of
B0r(h/2p). For a nucleus with I=1/2, the energy difference between two states
is
ΔE=E-1/2-E+1/2 = B0 r(h/2p)
m=–1/2
m=+1/2
The Zeeman splitting is proportional to the strength of the magnetic
field 7
Boltzmann distribution
Quantum mechanics tells us that, for net absorption of radiation to occur,
there must be more particles in the lower-energy state than in the higher one. If
no net absorption is possible, a condition called saturation.
When it’s saturated, Boltzmann distribution comes to rescue:
Pm=-1/2 / Pm=+1/2 = e -DE/kT
where P is the fraction of the particle population in each state,
T is the absolute temperature,
k is Boltzmann constant 1.381*10-28 JK-1
Example: At 298K, what fraction of 1H nuclei in 2.35 T field are in the upper and lower
states? (m=-1/2 : 0.4999959 ; m=1/2 : 0.5000041 )
The difference in populations of the two states is only on the order of few
parts per million. However, this difference is sufficient to generate NMR signal.
Anything that increases the population difference will give rise to a more
intense NMR signal.
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