“ELECTRON SPIN RESONANCE

SECTROSCOPY”

- Dr. Poonam Khandelwal

1
“ELECTRON SPIN RESONANCE SECTROSCOPY”

Introduction
B0 B0

 0  B0  0  B0
 0  B0  0  B0
Electron paramagnetic Resonance (EPR), often called Electron Spin Resonance
(ESR) was discovered by Soviet physicist „Zavoisky‟ in 1945.

ESR is a branch of absorption spectroscopy in which electromagnetic

radiation having frequency in the microwave region is absorbed by paramagnetic
substances to induce transitions between magnetic energy levels of electrons with
unpaired spin i.e. electronic spin S < 0. The magnetic energy splitting is done by
applying a strong static magnetic field, which is exposed to an orthogonal low
amplitude high frequency field. The free electron behave as a spinning, negatively
charged particle with a resulting magnetic moment. By virtue of its charge and
spin an electron acts as a bar magnet and can thus interact with an external
magnetic field.

Types of Substances with Unpaired Electrons :

a) Stable Paramagnetic Substances :
These include stable substances which can be studied very easily eg. NO,
O2 and No2 and transition metal ions and rare earth elements.

b) Unstable Paramagnetic Substances :

These can be produced either as the intermediate in chemical reaction or
by irradiation of stable molecules with a beam of nuclear particles or with
U.V. or X-ray radiation i.e. the free radicals or radicals ions.

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 THEORY OF ESR

i) ELECTRON BEHAVIOUR :
In ESR, the energy levels are produced by the interaction of the magnetic
moment of an unpaired electron in a molecule ion with an applied magnetic
field. The ESR spectrum results in due to the transitions between three
energy levels by absorbing radiation microwave frequency.

The magnetism of an electron can be expressed by saying that an electron

with a magnetic moment  which is proportional to e/m, where e and m
1
having their usual meanings has a spin, S= . This particle like proton has
2
1
2 magnetic energy levels. The lower level corresponds to m=  and
2

higher to m=  1
2

The magnetic moment thus given by:

 = -gs …. (1)
g = spectroscopic splitting factor
or g – factor or gyromagnetic ratio.
g = ~2 or 2.0023193
 = Bohr magneton
eh
i.e. =  9.2740 x10 24 J / T
4me
e & me being electronic charge and mass,
h = planck’s constant
When electrons placed in magnetic field they will have their energies
changed by certain number of ergs.
1
E = H = -gsH = + (gH) …. (2)
2
Where H = field strength of external magnetic field.

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 S.I. units = Tesla (T)
But in EPR gauss (1G = 0.0001T)
Thus the difference in energy E between the two levels is given by
E = gH = h  …. (3)
The overall magnetic momentum, eff can be expressed via overall
angular momentum. J & g values :
1
eff = g [J(J+1)] 2
…. (4)

In ESR spectroscopy unlike others, there is splitting of the energy levels

and hence the frequency capable of causing transitions between these
levels is a function of magnetic field strength H.

For the unpaired electrons there are thus 2 energy levels.

The population difference between the two energy levels of a sample

having unpaired electrons in the thermodynamic equation in magnetic field
is given by Boltzman law :
n1 E  gH
 exp   exp …. (5)
n2 kT kT
n1 and n2 = population in upper and lower level respectively.
Ms+½

Ms=+½ E=h  =geH0

H=0
Energy

Hz  0 Ms=–½

a) Absorption
Spectrum Hz

b) Derivative
spectrum

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 ENERGY LEVEL DIAGRAM SHOWING ESR SPECTRUM

n2 electron
S=–½

½gH
n1+n2 electrons
E=gH=h 
H=0
½gH
Energy level for
Zero Magnetic S=+½
field
n1 electron

ENERGY LEVELS FOR MAGNETIC FIELD H

Energy levels in ESR spectroscopy

When radiation is supplied to the sample of frequency 2 in such a manner

that energy between the electron states (i.e. h  =E=gH), then resonance

occur.

ii) THE G-FACTOR:

The g-actor is one of the important quantities determined from the ESR

spectra of odd-electron systems.

The value for g for an unpaired electron in gaseous atom or ion, for which

Russel-Saunders coupling is applicable is given by the expression.

1  J ( J  1)  S ( S  1)  L( L  1)
g
2 J ( J  1)

For a free electron (S=½, L=0, J=½) value of g=2.0 is easily calculated from

the above equation. Thus the actual value is 0.0023 due to relativistic

correction. From the relation

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  = gHo/h, we see that

G = h  /Ho.

Thus, the g-factor is essentially a measure of the ratio between frequency

and magnetic field, for the free electron g has a value 2.0023. The organic

radicals such as methyl radical, have the g-value very close to the free

electron g-value molecule containing the unpaired electron with respect to

the magnetic field.

In a solution or in the gas phase, g is averaged over all orientations

because of the free motion of the molecules, but in a crystal movement is

restricted. If the paramagnetic radicals or ion is located in a perfectly cubic

crystal site (eg. Octahedral or tetrahedral site), the g-value is independent

of the orientation of the crystal and is said to be isotropic.

In a crystal site of lower symmetry the g-value depends upon the

orientation of the crystal is said to be anisotropic.

The gz value is equivalent to g||, the g value obtained when z axis is parallel

with the external magnetic field. The g value along x and y axes are gx and

gy, which in a tetragonal site are equal and referred to as g, the g-value

thus obtained with the external magnetic field perpendicular to the z-axis. If

 is angle between magnetic field and z axis, the experimental g value is

given by the following equation for a system with axial symmetry.

g2 = g||2 Cos2+g2sin2

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iii) HYPERFINE SPLITTING :
The detection of electron spin resonance signal proves the presence of

unpaired electrons in the sample. The intensity of the absorption line is

proportional to the number of unpaired electrons. The ESR spectroscopy

has been widely used in studying various photochemical, electro-chemical

reaction proceeding via free radical mechanism because of the presence of

hyperfine structure which is the result of the interaction between the

unpaired electrons and magnetic nuclei in the paramagnetic species. It

further gives two important informations:

1) It tells about the environment of the molecule and distribution of the

electron density within the molecule.

2) It allows identification of paramagnetic substance in number of cases.

The resonance frequency of an electron actually depends upon the

magnetic field at the electron and electron infact is affected by the applied

field, Ho and any local field due to magnetic fields of nuclei, Hlocal.

Thus the equations :

E = gH = h  becomes

h = g. (HO+Hlocal)

The effect of magnetic moments of nuclei on ESR spectrum is known as

hyperfine interaction and is responsible for splitting of ESR line, giving

rise to hyperfine structure.

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When an unpaired electron comes in the vicinity of a nuclear with a spin I,

an interaction takes place which causes the absorption signal to be split

into 2I+1 components, where I is the spin quantum number of the nucleus.

The cause of splitting in an isotropic system is the nuclear spin electron

spin coupling arising mainly from the Fermi contact term.

This effect is simply illustrated by considering as an example of hydrogen

atom (I=½ for the proton). The proton thus has a magnetic moment and the

electron will be affected by the magnetic field of the nucleus (a proton) as

well as that of the applied magnetic field. The energy of the electron will be

modified by the orientation of the magnetic moment of the proton which can

also be parallel or antiparallel to the magnetic field.

The relative orientation of the nuclear magnetic moment and the electron

magnetic moment causes a splitting of original 2 level to 4 level.

THE SELECTION RULE FOR THE HYPERFINE TRANSITION IS:


ms=+1, mI=0

This selection rule may be interpreted by saying that the nuclear motion is

much slower than the electronic motion so that during the time electron

changes its spin orientation, the nucleus, being heavier has no time to

reorient its spin so that mI=0

The EPR spectrum of a Hydrogen atom in a solid matrix consists of 2

peaks of equal intensity centered at g=2.0023. The two-energy levels of a

free electron in a magnetic field are shown in the Figure with ms=–½

aligned with the field and ms=+½ aligned opposed to the field. (The

spectrum of a free electron would consist of a single peak corresponding to

a transition between these levels).

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 For each value of electron spin angular momentum quantum number ms,

the nuclear spin angular momentum quantum number mI, can have values

of +½, giving rise to four different energy levels.

INTERACTION OF UNPAIRED ELECTRON WITH ONE PROTON

Possible orientations of electrons and nuclear magnetic moments

S  ½ S  ½ S ½ S ½
a)        
 
I ½  
I ½
 
I ½
 
I ½

Splitting of energy levels

b)
I=+½
S= –½

I=–½

No applied field
I=–½

S=+½
I=+½
Field Ho
Field Ho
No Proton
Interaction
with Proton
c) Splitting of Spectral Line

No Proton

aH

Interaction with
One Proton
Ho

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 When the interaction between the 2 energy states and the nuclear spin due
to proton is considered, each energy state is further split up into energy
levels corresponding to mI=+½ & mI=–½ when mI is nuclear spin angular
momentum quantum number. Thus two hyperfine lines are observed
(splitting of original line into a doublet results) and the energy difference
between the two values of the field at which the lines occur is called the
hyperfine splitting constant.

The energies of 4 energy levels are :

E½ , ½ = ½gH + ¼ 
E½ , –½ = ½gH – ¼ 
E–½ , –½ = –½gH + ¼ 
E–½ , ½ = –½gH – ¼ 

The general expression for all the four energy level is

E = gHms +  msmI
 = hyperfine coupling constant. Usually measured in gauss such as MHz
or cm–1.

The magnitude of the splitting, expressed in terms of coupling constant

 depends on following factors :

1) The ratio of the nuclear magnetic moment to the nuclear spin.

2) The electron spin density in the immediate vicinity of nucleus (Fermi
contact interaction).
3) An anisotropric effect.

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HYPERFINE SPLITTING IN CASE OF METHYL RADICAL (CH3)
Possible Nuclear spin arrangements of protons in a Methyl Radical.

Addition of the nuclear spin angular momentum quantum nos. of individual

protons results in four different values for total nuclear spin moment.

Here S = ½ & 3 equivalent protons. since for a proton I = ½, it is evident

that for three equivalent protons mI=+3/2, +½, –½, –3/2. Also ms=+½. This
ESR spectrum contains four equally spaced lines i.e. a quartet 1:3 : 3 :1

The hyperfine structure in the ESR spectrum of methyl radical CH3

MI
+ 3/2
+½
Ms
+½
–½
– 3/2

Ms=+½
Energy

H=0 – 3/2
–½
–½
H 0
+½
– 3/2
H 0
HFS=0

3 : 3
1: :1

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 Thus the spectra expected for differing number of equivalent protons can
be easily predicted by considering the splitting due to each proton in turn as
illustrated in the given figure.

+2 (1)
3
+ /2 (1)
+1(1) +1 (4)
MI=+½ +½ (3)
Ms=+½ 0 (2) 0 (6)
MI=–½ –½ (3)
–1 (1) –1 (4)
– /2 (1)
3

–2 (1)
Ms=+½
–2 (1)
– /2 (1)
3

–1(1) –1 (4)
ENERGY

MI=+½ –½ (3)
Ms=–½ 0 (2) 0 (6)
MI=–½ +½ (3)
+1 (1) +1 (4)
3
+ /2 (1)
+2 (1)

1 2 3 4

NO. OF PROTONS

Hyperfine energy level resulting from interaction of an unpaired

electron with varying numbers of equivalent protons

 In general, the total No. of peaks expected for an electron delocalised

Caused over n “equivalent protons‟” is given by n+1 (i.e. 2n I+1) and
the relative intensities of peaks given by the coefficients of binomial
expansion. (i.e. restricted strictly to the equivalent protons).

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 When signal is split by 2 equivalent protons, total mI for three levels has

m I  1, 0,  1

(mI=0 can have two values  ½  ½,½ & ½ the centre level is doubly
degenerate. Thus 3 peaks observed in the spectrum (mI=0 and
ms=1) intensity ratio = 1:2:1

 If in case the odd electron is delocalized over two sets of

“nonequivalent protons”, the number of lines thus expected is the
product of number expected [(2nII + 1) (2m IJ+1)]

e.g in case of naphthalene negative ion i.e. prepared by adding sodium to

naphthalene contains an odd electron which is delocalized over the entire
naphthalene ring.

 

 

 
 

In this case there are two sets of ( & ) of 4 equivalent protons each. A
natal of n+1 or 5 peaks expected for an electron delocalized on either of 4
equivalent protons.

i.e. [(2 x 2+1) x (2 x 2+1)]

= [(4+1) x (4+1)]
= 25 lines

Thus the ESR spectrum would show 25 lines.

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  The above rules and examples are for the nuclei with I = ½. But if
the electron is delocalized on nuclei with spin greater than ½ i.e. I
> ½, other rules apply.

For eg. Interaction with a single nitrogen nucleus (N14). I = 1, will cause a
splitting (2I +1) = 2 x 1 + 1 =3
i.e. 3 lines (triplet) of equal intensity i.e. 1:2:1 is observed.

The above is if the electron is delocalized over equivalent nuclei.

Interaction of unpaired Electron with two equivalent Protons

S = +½ S=–½
a)        
      
             
             
I=+1 I = 0 I = 0 I = -1 I=+1 I = 0 I = 0 I = -1

I = +1
S=–½
I=0

I = –1
b)

H0=0
I = –1

I=0
S=+½
H0 I = +1
No Proton
H0 interaction
with 2 Equivalent
Proton

c)

aH

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 BIBLIOGRAPHY
1. Russel, S. Drago, Physical Methods in Inorganic Chemistry, East
West Press, New York, 1971.

2. D.F. Shriver & Atkins, Inorganic Chemistry, Oxford University Press,

3rd Ed., 1999.

3. B.K. Sharma, Instrumental Methods of Chemical Analysis, Meerut,

20th Ed; 2001.

4. Gurdeep Chatwal & Sham Anand; Instrumental Methods of

Chemical Analysis, Himalaya Publishing, Bombay; Ed., 1996.

5. Puri, Sharma & Pathania, Principles of Physical Chemistry, Vishal

Publishing Co., Ed., 2004.

6. Bodie Douglass; “Concepts & Models of Inorganic Chemistry”, John

Wiley & Sons, Singapore, 3rd Edition.

7. P.F. Knowles, D. Marsh & H.W.E. Rattee “Magnetic Resonance of

Biomolecules”, John Wiley & Sons, London, 1976.

8. M.C.R. Symons, “Chemical & Biochemical, Aspects of Electron-Spin

Resonance Spectroscopy, Van Nostrand, Reinhold, New York
(1978).

9. Pure & Appl. Chem., Vol. 62, No. 6 pp. 1051-1054, 1990. Printed in
Great Britain.

10. Kurt Warncke, Jennifer C. Schmidt and Shyue-Chuke, J.A.C.S.,

2001-123, 3358.

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