Вы находитесь на странице: 1из 24

n Nuclear Magnetic Resonance

NMR

CHY 416 Organic Chemistry


Prof. Dr. Ali Hashem Essa
Lecture 2

What is NMR?
How does NMR work?
How is a three dimensional structure elucidated?
The net magnetization vector

β
Low energy gap
Bo > 0 ΔE = h ν
α
Bo = 0
One Level is more populated than the other
Therefore a Resulting Net Magnetization will be Macroscopically
Observable

Prof. Dr. Ali Hashem Essa Department of Chemistry


Theory of NMR

Classical Description

• Spinning particle precesses around an applied magnetic field

A Spinning Gyroscope
in a Gravity Field

m
cos ϕ =
I ( I + 1)

Prof. Dr. Ali Hashem Essa Department of Chemistry


Classical Description
• Net Magnetization
Ø Nuclei either align with or against external magnetic field along the z-axis.
Ø Since more nuclei align with field, net magnetization (Mo, MZ) exists parallel
to external magnetic field.
§ Net Magnetization along +Z, since higher population aligned with Bo.
§ Magnetization in X,Y plane (MX,MY) averages to zero.

z z

Mo
x x

y y
Bo Bo

Prof. Dr. Ali Hashem Essa Department of Chemistry


An NMR Experiment
resonant condition: frequency (ω1) of B1 matches Larmor frequency (ωo)
energy is absorbed and population of α and β states are perturbed.

z z

Mo B1 off…
x x
B1
(or off-resonance) Mxy
ω1
y y
ω1

And/Or: Mo now precesses about B1 (similar to Bo)


for as long as the B1 field is applied.
Again, keep in mind that individual spins flipped up or down
Right-hand rule
(a single quanta), but Mo can have a continuous variation.

Prof. Dr. Ali Hashem Essa Department of Chemistry


Concept 1: When the B1 field is turned on, the net magnetization
rotates down into the XY plane

Bo

Prof. Dr. Ali Hashem Essa Department of Chemistry


Concept 2: When the B1 field is turned off, the net magnetization
relaxes back to the Z axis with the time constant T1
That generate Larmor frequency

z
T
1
Bo

T1 is the “longitudinal” relaxation time constant


which results from “spin-lattice” relaxation

Prof. Dr. Ali Hashem Essa Department of Chemistry


Concept 3: Individual spins precess about the magnetic field axis.

Bo

Precession frequency = Larmor frequency


ωo = -γ Bo (MHz)

Prof. Dr. Ali Hashem Essa Department of Chemistry


Concept 4: After magnetization is rotated into the xy plane by the B1 field
produced from a pulse through the coil, it will precess in the xy plane.

y
z

Bo
x
x

Prof. Dr. Ali Hashem Essa Department of Chemistry


Concept 5: The individual magnetization vectors whirling around in the xy
plane represent a changing magnetic field and will induce a current in the
sample coil which has its axis along the x-axis.

y y

Prof. Dr. Ali Hashem Essa Department of Chemistry


Concept 6: NMR signal is a Fourier transform of the oscillating
current induced in the sample coil

x
y y
-y
-x

time

frequency

Prof. Dr. Ali Hashem Essa Department of Chemistry


NMR Relaxation
a) No spontaneous reemission of photons to relax down to ground state
Probability too low à cube of the frequency

b) NMR signal relaxes back to ground state through two distinct processes

Prof. Dr. Ali Hashem Essa Department of Chemistry


z

Mo
x
= Net magnetization
B1
y
ω1 z

β β
If we apply a
x
90⁰ Rf pulse Bo > 0
Bo > 0

α α

z
β If we apply a β

more powerful Bo > 0


Bo > 0 x

Rf pulse (180 ⁰) α
α

Prof. Dr. Ali Hashem Essa Department of Chemistry


An NMR Experiment
What Happens Next?
The B1 field is turned off and Mxy continues to precess about Bo at frequency ωo.
z

Mxy ωo
y

Receiver coil (x)


Þ NMR signal
FID – Free Induction Decay
Mxy is precessing about z-axis in the x-y plane
Time (s)

y y y

Prof. Dr. Ali Hashem Essa Department of Chemistry


NMR Signal Detection - Fourier Transform

So, the NMR signal is collected in the Time - domain

Fourier
Transform

But, we prefer the frequency domain.

Fourier Transform is a mathematical procedure that


transforms time domain data into frequency domain

Prof. Dr. Ali Hashem Essa Department of Chemistry


NMR Spectrometry: Excitation & Relaxation

A low-energy nuclei (aligned with the applied field) will jump to a high energy
spin state (opposing the applied field) when given a pulse of RF. (Excitation)
Against
field

RF signal coil With detector coil


field can be the same coil!

Induced signal

When the magnetic field is removed, the nuclei revert back to their original
state releasing the energy that was just given to them in the form of
radiation. (Relaxation)
The cycle of excitation and relaxation of the nucleus is called resonance –
hence the name NMR...nuclear magnetic resonance.

Prof. Dr. Ali Hashem Essa Department of Chemistry


Classical Description

• Observe NMR Signal


Ø Remember: a moving magnetic field perpendicular to a coil will induce a
current in the coil.
Ø The induced current monitors the nuclear precession in the X,Y plane

Detect signal along X

RF pulse along Y
ν = γBo/2π

Prof. Dr. Ali Hashem Essa Department of Chemistry


CW Continous Wave

Prof. Dr. Ali Hashem Essa Department of Chemistry


Prof. Dr. Ali Hashem Essa Department of Chemistry
NMR Sensitivity

But at a significant cost!

~$800,000 ~$2,000,000 ~$4,500,000

Prof. Dr. Ali Hashem Essa Department of Chemistry


NMR Spectrometer

Varian A-60 spectrometer(1961) Bruker AV500 spectrometer(1999)

Prof. Dr. Ali Hashem Essa Department of Chemistry


2 Helmholtz Coils:
1 inside the other;
for tube NMR

Solenoidal
Microcoil
for flow NMR

Prof. Dr. Ali Hashem Essa Department of Chemistry


ΔE depends on the applied Bo

Prof. Dr. Ali Hashem Essa Department of Chemistry

Вам также может понравиться