Electron Spin Resonance

Atharva Vibhute
SC18B141
• When
  magnetic field is applied to an unpaired electron,
then the two possible spin configurations have different
energies.
• U =-μ.B
• U=gμBBms ;ms = ; g = 2.00232
• J/T
• for B= 1 mT
• v = Hz
Problems
•1.  The frequency is in GHz - not possible to detect with
photographic plates

2. The above calculation is true for free electrons - but free

electrons are not availaible.
• Electron’s envoironment affects value of g.
• value of g 1.9-2
• The electron must be unpaired.
Solutions
• Unpaired electrons can be found in transition metal ions,
ions like H2O+ and free radicals.
• To excite and find the frequency of excitation we use the
following circuit.
Data fitting
•   V ; V = coil voltage
B
• v B
• v V
• Proportionality constant
was found to be,
• 10.2218 MHz/V
• g for DPPH can be
calculated from this.
Application : Detection of free radicals

• Radicals at very low concentrations(10-8 M) can be

detected.
• ESR detection of a free radical intermediate during the
peroxidase-catalyzed oxidation of the antimalarial drug
primaquine.
• ESR is used for dating of teeth.
• radicals like Reactive oxygen species can be detected in
plants which are associated with stress.
How are they detected?
• The free electron has only one line in ESR sspectrum.
• But in molecules the electron spin couples with the
surrounding nuclear spins
• This gives multiple energy states.
• The spectral line spacing is related to the hyperfine
coupling constant of the nucleus.
• Hence we have unique spectrums.
• For a radical having M1 equivalent nuclei, each with a spin
of I1, and a group of M2 equivalent nuclei, each with a spin
of I2, the number of lines expected is (2M1I1 + 1) (2M2I2 +
1).
• The sample is radiated with a frequency and magnetic
field is scanned to get the spectrum.
• So this spectrum can be compared with the
EPR spectral profiles and the radical can be
found out.
Spin trapping
• Some radicals are very shortlived.
• Not enough time to do ESR spectroscopy.
• These radicals are reacted with an unsaturated
compound (C-nitroso or nitrone) to give a new radical with
a longer lifetime, known as a spin adduct.
Thank You