Epr - Interpretation Introduction Proportionality Factor (G-Factor) Hyperfine Interactions Easyspin Simulations References Problems

Content
 EPR – Interpretation
 Introduction
 Proportionality factor (g-factor)
 Hyperfine Interactions
 EasySpin Simulations
 References
 Problems
EPR - Interpretation
Electron paramagnetic resonance spectroscopy (EPR), also called electron

spin resonance (ESR), is a technique used to study chemical species with
unpaired electrons. EPR spectroscopy plays an important role in the
understanding of organic and inorganic radicals, transition metal complexes,
and some biomolecules. For theoretical background on EPR, please refer
to EPR:Theory.
Introduction
Like most spectroscopic techniques, EPR spectrometers measure the

absorption of electromagnetic radiation. A simple absorption spectra will
appear similar to the one on the top of Figure 1. However, a phase-sensitive
detector is used in EPR spectrometers which converts the normal absorption
signal to its first derivative. Then the absorption signal is presented as its first
derivative in the spectrum, which is similar to the one on the bottom of
Figure 1. Thus, the magnetic field is on the x-axis of EPR spectrum; dχ″/dB,
the derivative of the imaginary part of the molecular magnetic susceptibility
with respect to the external static magnetic field in arbitrary units is on the y-
axis. In the EPR spectrum, where the spectrum passes through zero
corresponds to the absorption peak of absorption spectrum. People can use
this to determine the center of the signal. On the x-axis, sometimes people
use the unit “gauss” (G), instead of tesla (T). One tesla is equal to 10000
gauss.
Figure 1.
Comparison of absorption spectrum and EPR spectrum. Image used with
permisison (Public Domain).
Proportionality factor (g-factor)
As a result of the Zeeman Effect, the state energy difference of an electron

with s=1/2 in magnetic field is
ΔE=gβB(1)(1)ΔE=gβB
where β is the constant, Bohr magneton. Since the energy absorbed by the
electron should be exactly the same with the state energy difference ΔE,
ΔE=hv ( h is Planck’s constant), the Equation 11 can be expressed as
hν=gβB(2)(2)hν=gβB
People can control the microwave frequency v and the magnetic field B. The
other factor, g, is a constant of proportionality, whose value is the property of
the electron in a certain environment. After plugging in the values of h and β
in Equation 22, g value can be given through Equation 33:
g=71.4484v(in GHz)/B (in mT)(3)(3)g=71.4484v(in GHz)/B (in mT)
A free electron in vacuum has a g value g e= 2.00232. For instance, at the

magnetic field of 331.85 mT, a free electron absorbs the microwave with an
X-band frequency of 9.300 GHz. However, when the electron is in a certain
environment, for example, a transition metal-ion complex, the second
magnetic field produced by the nuclei, ΔB, will also influence the electron.
At this kind of circumstance, Equation 22 becomes
hν=gβ(Be+ΔB)(4)(4)hν=gβ(Be+ΔB)
since we only know the spectrometer value of B, the Equation 44 is written
as:
hν=(ge+Δg)βB](5)(5)hν=(ge+Δg)βB]
From the relationship shown above, we know that there are infinite pairs of v
and B that fit this relationship. The magnetic field for resonance is not a
unique “fingerprint” for the identification of a compound because spectra can
be acquired at different microwave frequencies. Then what is the fingerprint
of a molecule? It is Δg. This value contains the chemical information that lies
in the interaction between the electron and the electronic structure of the
molecule, one can simply take the value of g = g e+ Δg as a fingerprint of the
molecule. For organic radicals, the g value is very close to ge with values
ranging from 1.99-2.01. For example, the g value for •CH3 is 2.0026. For
transition metal complexes, the g value varies a lot because of the spin-orbit
coupling and zero-field splitting. Usually it ranges from 1.4-3.0, depending
on the geometry of the complex. For instance, the g value of Cu(acac)2 is
2.13. To determine the g value, we use the center of the signal. By using
Equation 33, we can calculate the g factor of the absorption in the spectrum.
The value of g factor is not only related to the electronic environment, but
also related to anisotropy. About this part, please refer to EPR:Theory,
Parallel Mode EPR: Theory and ENDOR:Theory. An example from UC
Davis is shown below[1] (Britt group, Published in J.A.C.S. ):
Figure 2. EPR
spectra of some proteins (WT mitoNEET, H87C mitoNEET, and ferredoxin).
Frequency is 30.89 GHz.1
Hyperfine Interactions
Another very important factor in EPR is hyperfine interactions. Besides the

applied magnetic field B0, the compound contains the unpaired electrons are
sensitive to their local “micro” environment. Additional information can be
obtained from the so-called hyperfine interaction. The nuclei of the atoms in
a molecule or complex usually have their own fine magnetic moments. Such
magnetic moments occurrence can produce a local magnetic field intense
enough to affect the electron. Such interaction between the electron and the
nuclei produced local magnetic field is called the hyperfine interaction. Then
the energy level of the electron can be expressed as:
E = gmBB0MS + aMsmI (6)
In which a is the hyperfine coupling constant, mI is the nuclear spin quantum

number. Hyperfine interactions can be used to provide a wealth of
information about the sample such as the number and identity of atoms in a
molecule or compound, as well as their distance from the unpaired electron.
Table 1. Bio transition metal nuclear spins and EPR hyperfine patterns[3]
The rules for determining which nuclei will interact are the same as
for NMR. For isotopes which have even atomic and even mass numbers, the
ground state nuclear spin quantum number, I, is zero, and these isotopes have
no EPR (or NMR) spectra. For isotopes with odd atomic numbers and even
mass numbers, the values of I are integers. For example the spin of 2H is 1.
For isotopes with odd mass numbers, the values of I are fractions. For
example the spin of 1H is 1/2 and the spin of 23Na is 7/2. Here are more
examples from biological systems:
Table 2. Bio ligand atom nuclear spins and their EPR hyperfine patterns[3]
The number of lines from the hyperfine interaction can be determined by the
formula: 2NI + 1. N is the number of equivalent nuclei and I is the spin. For
example, an unpaired electron on a V4+ experiences I=7/2 from the vanadium
nucleus. We can see 8 lines from the EPR spectrum. When coupling to a
single nucleus, each line has the same intensity. When coupling to more than
one nucleus, the relative intensity of each line is determined by the number of
interacting nuclei. For the most common I=1/2 nuclei, the intensity of each
line follows Pascal's triangle, which is shown below:
Figure 3. Pascal's triangle
For example, for •CH3, the radical’s signal is split to 2NI+1= 2*3*1/2+1=4
lines, the ratio of each line’s intensity is 1:3:3:1. The spectrum looks like this:
Figure 4. Simulated EPR spectrum of the •CH3 radical.

en.Wikipedia.org/wiki/File:EPR_methyl.png
If an electron couples to several sets of nuclei, first we apply the coupling

rule to the nearest nuclei, then we split each of those lines by the coupling
them to the next nearest nuclei, and so on. For the methoxymethyl radical,
H2C(OCH3), there are (2*2*1/2+1)*(2*3*1/2+1)=12 lines in the spectrum,
the spectrum looks like this:
Figure
5. Simulated EPR spectrum of the H 2C(OCH3)
radical. http://en.Wikipedia.org/wiki/File:EP...hoxymethyl.png
For I=1, the relative intensities follow this triangle:
Figure 5. Relative Intensities of each line when I=1
The EPR spectra have very different line shapes and characteristics
depending on many factors, such as the interactions in the spin Hamiltonian,
physical phase of samples, dynamic properties of molecules. To gain the
information on structure and dynamics from experimental data, spectral
simulations are heavily relied. People use simulation to study the
dependencies of spectral features on the magnetic parameters, to predict the
information we may get from experiments, or to extract accurate parameter
from experimental spectra.
EasySpin Simulations
Many methods were developed to simulate the EPR spectra. Dr. Stefan Stoll
wrote EasySpin, a computational EPR package for spectral simulation.
EasySpin is based on Matlab, which is a numerical computing environment
and fourth-generation programming language. EasySpin is a powerful tool in
EPR spectral simulation. It can simulate spectra under many different
conditions. Some functions are shown below:
Spectral simulations and fitting functions:
 garlic: cw EPR (isotropic and fast motion)
 chili: cw EPR (slow motion)
 pepper: cw EPR (solid state)
 salt: ENDOR (solid state)
 saffron: pulse EPR/ENDOR (solid state)
 esfit: least-squares fitting
To learn more, please visit EasySpin: http://www.easyspin.org/.

References
1. Dicus, M.M; Conlan,A.; Nechushtai,R.; Jennings,P.A.;Paddock,M.L.;

Britt,R.D.; Stoll S. J. AM. CHEM. SOC. 2010, 132, 2037–2049
2. Hagen,W.R. 2009. Biomolecular EPR Spectroscopy. Boca Raton: CRC
Press.
3. Hagen,W.R. Dalton Trans., 2006, 4415–4434
4. Stoll,S., Schweiger,A. Journal of Magnetic Resonance 178 (2006) 42–
55
Problems
1. If there is one unpaired electron in Cu2+ (I=3/2) and the copper ion is

coordinated by one nitrogen atom (I=1) and one OH- (I=1/2), how
many lines can be expected in the EPR spectrum?
( (2*1*3/2+1)*(2*1*1+1)*(2*1*1/2+1)=24 )
2. For a radical, the magnetic field is 3810 G, the frequency of the
microwave is 9600 MHz. What is the value of its g-factor?
g=(71.4484)(9600x10−3)3810x10−1=1.800(6)(6)g=(71.4484)
(9600x10−3)3810x10−1=1.800
Contributors and Attributions
 Pei Zhao (University of California, Davis)

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 Proportionality factor (g-factor)

Electron paramagnetic resonance spectroscopy (EPR), also called electron

Like most spectroscopic techniques, EPR spectrometers measure the

As a result of the Zeeman Effect, the state energy difference of an electron

g=71.4484v(in GHz)/B (in mT)(3)(3)g=71.4484v(in GHz)/B (in mT)

A free electron in vacuum has a g value g e= 2.00232. For instance, at the

Another very important factor in EPR is hyperfine interactions. Besides the

E = gmBB0MS + aMsmI (6)

In which a is the hyperfine coupling constant, mI is the nuclear spin quantum

Figure 4. Simulated EPR spectrum of the •CH3 radical.

If an electron couples to several sets of nuclei, first we apply the coupling

For I=1, the relative intensities follow this triangle:

Figure 5. Relative Intensities of each line when I=1

Spectral simulations and fitting functions:

 garlic: cw EPR (isotropic and fast motion)

 chili: cw EPR (slow motion)

 pepper: cw EPR (solid state)

 saffron: pulse EPR/ENDOR (solid state)

 esfit: least-squares fitting

To learn more, please visit EasySpin: http://www.easyspin.org/.

1. Dicus, M.M; Conlan,A.; Nechushtai,R.; Jennings,P.A.;Paddock,M.L.;

1. If there is one unpaired electron in Cu2+ (I=3/2) and the copper ion is

 Pei Zhao (University of California, Davis)

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