Theory

When a molecule or compound with an unpaired electron is placed in a strong

magnetic field, the spin of the unpaired electron can align in two different ways
creating two spin states, ms = . The alignment can either be along the direction
(parelle) to the magnetic filed which corresponds to the lower energy state ms = - or
opposite (antiparallel) to the direction of the applied magnetic field ms = + . The two
allignments have different energies and this difference in energy lifts the degeneracy of
the electron spin states. The energy difference is given by:
E = E+ - E- = hv = gmB

h = Plancks constant (6.626 x 10-34 J s-1),

v = the frequency of radiation,
= Bohr magneton (9.274 x 10-24 J T-1),
B = strength of the magnetic field in Tesla,
g = the g-factor (more explanation on g factor)
During the experiement the values of h, v, and does not change and g value decrease
as B increases. The g-factor is a unitless measurement of the intrinsic magnetic
moment of the electron, and its value for a free electron is 2.0023. The concept of g can
be roughly equated to that of chemical shift in NMR. EPR spectrum is the absorption of
microwave frequency radiation ploted against the magnetic field intensity
3.1. Working principles of EPR:
In an EPR experiment the field of the spectrometer magnet is swept linearly to excite
some of the electrons in the lower energy level to the upper energy level while the
sample is exposed to fixed microwave irradiation. The free or the upaired electrons
have a small magnetic field and orient themselves parallel to the larger field produced
by the spectrometers magnet. At a particular magnetic field strength the microwave
irradiation will cause some of the free electrons to flip and orient against the
spectrometers magnetic field. This separation between the lower and the higher
energy level is exactly matched by our microwave frequency. The condition where the
magnetic field and the microwave frequency are just right to produce an EPR
resonance (or absorption) is known as the resonance condition is detected by the
spectrometer., EPR spectroscopy can be carried out by either
varying the magnetic field and holding the frequency constant or
varying the frequency and holding the magnetic field constant (as is the case for NMR
spectroscopy).
Typically in a comericial spectrometer works by varying the magnetic field and holding
the frequency constant. EPR spectrometers working at frequencies ranging from
several hundred MHz to several hundred Ghz are in use. 1-2 GHz (L-band) and 2-4 GHz
(S-band), 8-10 GHZ (X-Band), 35 Ghz (Q-band) and 95 GHz (W-band). The most
commonly used EPR spectrometer is in the range of 9-10 GHz (X-band).