Magnetic Resonance Spectroscopy

Ivor Allan Jake Denham-Dyson: 737213

October 27, 2016

Introduction

Spin is the intrinsic angular momentum of a particle, nuclear spin is the total angular momentum (I) of the
nucleus and is associated with a magnetic dipole moment mI . We can exploit the properties of a compounds
spin to determine some of its characteristics. By placing the compound in a magnetic field and allowing
its magnetic dipoles to align we can change the particles orientation by introducing energy into the system
through electromagnetic radiation, when the system re-emits the energy in the form of electromagnetic
radiation this can be observed and will indicate properties about the compound being studied. In this
experiment we wish to determine the g-factor of e and 1 H and investigate the spin-spin relaxation time
of e using magnetic resonance techniques.

Figure 1: The alignment of magnetic of magnetic dipoles in a magnetic field.

2
2.1

Theory
Nuclear spin and Magnetic Moments

Nuclear spin is either an integer, zero or half interger, magnetic moments are only present in nuclei where
the spin is non-zero and therefore a magnetic field will not cause nuclei of spin zero to align making the
experimental technique ineffective.
Mass Number
Even
Odd

Number of Protons
Even
Odd
Even
Odd

Number of Neutrons
Even
Odd
Odd
Even

Spin
0
Interger
Half-Interger
Half-Interger

Nuclear
p spin angular momentum is a vector first reported by Pauli in 1924 which has a magnitude given
by L = h
I(I + 1) and when projected onto the Z-axis takes on values m = I, I + 1, . . . , I 1, I. Thus
along he Z-axis the angular momentum is given by Lz = mh.

The potential energy of a an object possesing a magnetic moment in an external magnetic field is given by
E = B0
Where is given by,
= iA
= ir2
evr
=
2
This can be re-written in terms of the angular momentum (The minus sign is obtained from sin())
=

e
L
2me

Substituting this into the equation for potential energy one obtains the following
E=

e
LB0
2me

The maximun component along any direction of L is Lz and generally includes an orbital contribution
e
L and from our earlier discussion Lz = mh, hence we have
g = 1 written convetionally as g 2m
e
E = (hm)B0
e
Where = 2m
g and m = 12 in most cases giving
e

1
E = hB0
2
Resonance will occur at the energy equal to the difference of the separation levels
0 = E
h
h0 = |E E+ |

h0 = hB0

eh
gB0
h0 =

2me
h0 = B gB0

Where uB =

e
h
2me

(1)

is the Bohr magneton, simplifying we obtain

0 = B0

2.2

Relaxation Times

We wish to describe the population of up spins or down spins and take the approach of dimensional analysis.
Our single assumption is that the change in up/down spin population with respect to energy is dependent
on some way on the current population, temperature of the system and boltzmanns constant.
N+ := Up Spins (Number)
N := Down Spins (Number)
E := Energy (Joules)
T := Temperature (Kelvins)
kb := Energy per Temperature increment - Boltzmanns Constant (Joules.Kelvins1 )

(N+ J 1 )a (N+ )b (K)c (JK 1 )d = 1

P a+b J a+d K cd = 1

a+b=0
a + d = 0
cd=0
a = b
a=d
a=c
3


1
a
a
b a 1
= = a
c a 1
1
a
d

(2)

Let a = 1, we have from the Buckingham-Pi theorem H(1 ) = 0.

dN+
(ne )1 T kb + C0 = 0
dE
C1 ne
dN+
=
dE
T kb
dN+
C1
=
dE
N+
T kb
N+
C1
ln
=
E0 E1
N
T kb
C1 E
N+
= e T kb
N
C1 = 1 as kb is the energy per temperature increment or it can view as being absorbed into the value of kb
.
E
N+
= e kb T
N

Applying the Taylor Series we have

N+
hB0
=1+
N
kb T

(3)

The surroundings of the spin system in known as the lattice, because of the changes in population
due to to radio frequency electromagnetic radiation the system will briefly be out of equilibrium until this
energy is released into the lattice as illustrated in 3. The period over which this energy transfer takes
places and equilibrium is once again reached is known as the spin-lattice relaxation time denoted T1 and is
characteristic of the sample and particular experiment.

Figure 2: The alignment of magnetic of magnetic dipoles in a magnetic field.

2.3

Biot-Savart Law

Biot-Savart Law is given by,

B(r) =

0
4

Idl r

(4)

|r|

Figure 3: Magnetic field around a loop of wire.

0
4

Idl r

0
4

|r|
Idl sin 2

0
4

0
Bx (r) =
4

0
4

B(r) =
B(r) =
B(r) =

|r|
Idl
|r|

y-component cancels

Bx (r) =

Idl

2 sin
|r|
Idl R
2
|r| r

Using the pythagorean theorem.

r=

p
x2 + R 2

Around a circular loopm of wire we have

B(r) =

0 IR2
1
2 [R2 + x2 ] 23

If we take two loops with n inbetween them we find

R
)
2
n0 IR2

BHelmholtz = 2nB(
BHelmholtz =
BHelmholtz =
BHelmholtz

2.4

[R2 + ( R2 )2 ] 2
n0 IR2
3

[ 45 R2 ] 2
  32
4
n0 I
=
5
R

Paramagnetic Spin

As opposed to diamagnet materials paramagnetic materials are attracted in the direction of an external
magnetic field. Paramagnetic spin systems refer to an unpaired spin in the outer orbitals of atoms, compounds and molecules which is unaligned in the presence of a magnetic field but are attracted in the direction
of an external magnetic field.

Experimental Procedure

3.1

ESR Measurements

1. Set up a magnetic field by passing a current through the Helmholtz coils by settign the current to
roughly 0.19
2. Align the Lorentzian shaped curve on the oscilloscope to x = 0 and determine the frequency at which
resonance occurs.
3. Measure the frequency at which half the maximun of the peak occurs at both the left and right hand
side of the graph.
(a) Increase the current by 0.1A and repeat steps 2 and 3 recording both the current and frequency
values.

3.2

NMR Measurements

1. Set the frequency of the oscillating circuit at roughly 16.9MHz.

2. Bring the resonance signal in to view by adjusting the magnetic field and center it.
3. Record the resonance frequency and magnetic field through the use of a Hall probe.
(a) Repeat steps 2 and 3 by increasing the frequency by 0.1MHz to obtain 10 further readings.

Results

4.1
4.1.1

Electron Paramagnetic Resonance

Raw Data of ESR
Readings
1
2
3
4
5

4.1.2

L (MHz)
24.33
25.53
27.46
27.02
29.65

R (MHz)
30.44
29.86
31.30
32.78
32.79

4.2.1

I
0.1968
0.201
0.210
0.221
0.231

Raw Data of NMR

(MHz)
16.90670
17.02610
17.10675
17.20391
17.30251
17.40694
17.50473
17.60147
17.70663
17.80410
17.90212

4.2

C (MHz)
27.25
28.23
29.23
30.23
31.23

B0 (mT)
423
425
428
431
433
436
438
440
444
446
449

Calculate the g-factor of e

Define Data

Listing 1: Define ESR data

i = {0.1968 ,
vL = {24.33 ,
vR = {30.44 ,
vC = {27.25 ,

4.2.2

0.201 ,
25.53 ,
29.86 ,
28.23 ,

0.210 ,
27.46 ,
31.30 ,
29.23 ,

0.221 ,
27.02 ,
32.78 ,
30.23 ,

0.231};
29.65};
32.79};
31.23};

Convert Current to Magnetic Field

Listing 2: Use Biot-Savart Law to obtain corresponding magnetic field

itob [ current_ ] := (4/5)(3/2)*(324*1.3566*10 -6* current )/(8.02*10 -2)
b = Map [ itob , i ]

Which gives,
I
0.1968
0.201
0.210
0.221
0.231

B0 (T)
0.00077176
0.000788231
0.000823525
0.000866662
0.000905877

4.2.3

Calculate g-factor

Listing 3: Calculate g-factor from resonance frequency and aggregate Results

bohrmagneton = 9.27400968*10 -24
hbar = 1.054571800*10 -34
btoge [ magnetic_ , w0_ ] := ( w0 *106* hbar )/( magnetic * bohrmagneton )
get = Table [ btoge [ b [[ i ]] , vC [[ i ]]] , {i , 5}]
g = Mean [ get ]

We obtain ge = 0.400207

4.3
4.3.1

Determine T2 of e and plot the amplitude as a function of deviation of

frequency
Determine the linewidth and the reciprocal

Listing 4: Determine the linewidth and the reciprocal by finding the difference between
VR and VL
linewidth = vR - vL ;
reciprocallw = Map [1/# & , linewidth ];

Linewidth
6.11
4.33
3.84
5.76
3.14
4.3.2

Reciprocal (T)
0.163666
0.230947
0.260417
0.173611
0.318471

Plot the linewidth as a function of deviation of frequency

Listing 5: Plot
F [ lw_ , w0_ , w_ ] := 1/(1 + ( w - w0 )2*(2* lw )2)
Plot [{ F [ reciprocallw [[1]] , vC [[1]] , w ] ,
F [ reciprocallw [[2]] , vC [[2]] , w ] ,
F [ reciprocallw [[3]] , vC [[3]] , , w ] ,
F [ reciprocallw [[4]] , vC [[4]] , w ] ,
F [ reciprocallw [[5]] , vC [[5]] , w ]} , {w , 10 , 45} , PlotRange -> All ,
PlotLegends -> { " Reading 1 " , " Reading 2 " , " Reading 3 " , " Reading 4 " ,
" Reading 5 " }]

Figure 4: A plot of deviation from resonance frequency on the x-axis and amplitude on the y-axis

4.4
4.4.1

Nuclear Magnetic Resonance

Calculate the g-factor of 1 H

Listing 6: Define NMR data

fMHz = {16.90670 , 17.02610 , 17.10675 , 17.20391 , 17.30251 , 17.40964 ,
17.50473 , 17.60147 , 17.70663 , 17.80410 , 17.90212};
bmT = {423 , 425 , 428 , 431 , 433 , 436 , 438 , 440 , 444 , 446 , 449};
bT = Map [#1*10 -3 & , bmT ]*10 -4

Listing 7: Calculate g-factor from resonance frequency and aggregate Results

gyromagneticratiop = (1.6022*10 -19)/(2*1836*9.1*10 -31)
btogp [ magnetic_ , w0_ ] := ( w0 *106)/( magnetic * gyromagneticratiop )
gpt = Table [ btog [ bT [[ i ]] , fMHz [[ i ]]] , {i , 11}]
gp = Mean [ gpt ]

we obtain g1 H = 0.83405

4.5

Error

The error in ge and gp was found to be 0.000498527 and 0.000552237 through progation of errors.

Discussion

A g value for the proton and electron was obtained and a plot of the linewidth was obtained.
Looking at the fraction error in our answers we find
|2.0024 0.400207|
= 0.800136
|2.0024|
|5.58 0.83405|
error =
= 5.69025
|0.83405|
error =

10

Sources of error may have been human in that graphs were not perfectly aligned around the x = 0 point,
random errors could have occured due to electronic noise. We see in these results large errors however the
precision was good as many values for both were centered around the same value suggesting systematic
error of some sought.
The linewidth plots represented the shape and features around the resonance frequency accurately.

New Physics

Resonance techniques were a new way of probing the structure of matter and much was learned about
spin and and its relationship to angular energy. Helmholtz coils have been discussed before however their
usefulness in practical application has been shown clearly in this lab.

Bibliography
http://teaching.shu.ac.uk/hwb/chemistry/tutorials/molspec/nmr1.htm
http://www.rsc.org/learn-chemistry/wiki/Introduction to NMR spectroscopy
http://physics.tutorvista.com/modern-physics/nuclear-magnetic-resonance.html
http://www.brynmawr.edu/chemistry/Chem/mnerzsto/The Basics Nuclear Magnetic Resonance%20 Spectroscopy 2.htm
https://ia801406.us.archive.org/27/items/ExperimentsInModernPhysics/Melissinos-ExperimentsInModernPhysics.pdf
http://www.chemguide.co.uk/analysis/nmr/background.html
http://qudev.ethz.ch/content/courses/phys4/studentspresentations/nmr/James Fundamentals of NMR.pdf

http://chem.libretexts.org/Core/Physical and Theoretical Chemistry/Spectroscopy/Magnetic Resonance Spectroscopies/N

http://www.colby.edu/chemistry/PChem/lab/Spinlattice.pdf

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