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Principle:
The g-factor of a DPPH (Diphenyl-
pikrylhydrazyl) and the half-width of
the absorption line are determined,
using the ESR apparatus.
Options:
Teslameter, digital 13610.93 1 Electron spin resonance (ESR), model experiment.
Hall probe, tangent., prot. cap 13610.02 1
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Electron spin resonance 5.1.12
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5.1.12 Electron spin resonance
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Fig. 2a: Measuring bridge of the ESR apparatus. Fig. 3: The magnetic field B is compounded from a d.c. field
B= and an alternating field B, so that B = B= + B.
Through l=, B= is to be adjusted so that B= = Br.
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nating voltage modulation has been switched off, the two cur- In this case, HZ (2) can be written
rent values at which the moving spot crosses the x-axis can
be determined by slowly varying the d.c. current in the coil. HZ = mB gj B J (3)
The half-width of the signal is calculated from the difference
between these currents. with the Land factor
J 1J 12 S 1S 12 L 1L 12
gj 1
2J 1J 12
. (4)
Theory and evaluation
If an electron of mass m and charge eis located in an electro-
magnetic field with vector potential A and scalar potential f, Disregarding the influence of the nuclear spin, the energy
then its steady-state energy level and characteristic states are levels of HZ, for magnetic fields in the Z-direction, are
given by the solutions of the Dirac equation.
EZ = mB gj B mj
If the equation is solved for the c, component of the sate spi-
nor, it reads: with
1 p 2 mB 2 S B 2 p1 ec1
S S S mj = j, j 1, j.
(1)
where The selection rule for magnetic transitions of the electron spin
resonance experiment is
eh
mB (Bohr Magneton)
2mc % mj = 1
= 9.27 1027 Am2
so that the absorption condition reads
S
p S
S p e>c A mB gj B = % E = hf.
where p is the momentum, c the velocity of light, S the elec- In many cases, especially with molecular radicals, the angular
tron spin operator, and B = rot A is the magnetic field. momentum L of the unpaired electron is extinguished by the
h is Plancks constant electric fields of the neighbouring atoms and molecules. In the
case of DPPH, L = 0 and therefore
h = 6.626 1034 Js,
gj = 2.
and
11 1E>mc2 2 2 1E mc2 2
1
e In (3),
2
is approximately the excess of energy over the residual mass m = mB gj J (5)
energy.
is the magnetic
moment of an electron with the angular
For a free electron in a uniform magnetic field, the second momentum J in units of the Bohr magneton mB .
term (Zeeman term) interchanges with the first in the If account is also taken of the exchange of virtual photons be-
Hamiltonian operator of (1), and the energy level tween the electron and a radiation field in the static limit
through inclusion of the vertex corrections in increasing order,
e = eo + mB 2 Sz Bz, is obtained a modified abnormal magnetic moment of the electron is
obtained as a series in the fine-structure constant a:
if the z-axis lies in the direction of the magnetic field.
e2
a
eo is the energy of the electron without a magnetic field. hc
If the diamagnetic contribution from the first term of (1) is dis-
a2
m mB a 1 0.328 2 ... b gj J
S a S
regarded in the general case, then for the electron in a uniform (6)
magnetic field, the interaction Hamiltonian operator with the 2p p
magnetic filed, (Zeeman effect) is
The correction factor in the parentheses of equation (6) is
HZ = mB B ( L + 2 S ), (2) generally taken into account in gj, so that gj then 2.
Fig. 4 shows the energy level in the magnetic field B, for
where L and S are the operators of the orbital and spin angu-
DPPH.
lar momentum respectively. In addition, the spinorbit inter-
By supplying the corresponding energy, transitions can be
action
induced between the levels:
Hso = l S L
hf = gj mB H.
should be taken into account, so that only the total angular
momentum The probability of transtion depends on the occupation num-
ber and on the transition matrix elements. The latter are the
J = L + S same for absorption and emission processes.
Because of the interactions of the spins with the lattice or with
is a conservation value.
one another, the levels are not sharply defined, and this leads
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to a line width of the absorption spectrum and prevents an For the g-factor, one obtains:
equipartition of the levels (saturation) because of the corres-
ponding relaxation processes. 1
g = 10.43 ; Br in teslas
Br
The occupation numbers are given in accordance with the or
Boltzmann relation by:
1
gjmBB g = 2.507 ; Ir in amperes,
N2 E Ir
e kT e kT ,
N1 with the stated values.
where k is the Boltzmann constant. It is customary to take
account of other interactions in the constant g which vary A resonance current of 1.245 A was measured, corresponding
linearly B, e.g. the contact of Fermi interaction (WW) with the to a g-factor of 2.02, and a half-width value of 2.7 104 T.
nucleus, i.e.
(Literature values for DPPH:
g = gj (1 + WW), g = 2.0037, half-width 2.8 104 T).
wI
B = 0.6445 mo
R
on the axis of symmetry between the coils, where
Tm
mo = 1.256 106
A
With the numerical values stated, one obtains
T
B = 4.0642 103 i .
A
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