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    ESR and NMR

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    Umang Soni
    Spectroscopy is the experimental study of the absorption, emission, and scattering of electromagnetic radiation by atoms and molecules. There are several types of spectroscopy defined by the region of the electromagnetic spectrum used. This document focuses on electron spin resonance (ESR) spectroscopy, which involves the absorption of microwaves by unpaired electrons in a magnetic field. ESR provides information about electronic and magnetic properties as well as nuclear properties through analysis of hyperfine interactions. The major components of an ESR spectrometer are a microwave source, resonance cavity, magnet, and detector.

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    ESR and NMR

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    Umang Soni
    68 views20 pages
    Spectroscopy is the experimental study of the absorption, emission, and scattering of electromagnetic radiation by atoms and molecules. There are several types of spectroscopy defined by the region of the electromagnetic spectrum used. This document focuses on electron spin resonance (ESR) spectroscopy, which involves the absorption of microwaves by unpaired electrons in a magnetic field. ESR provides information about electronic and magnetic properties as well as nuclear properties through analysis of hyperfine interactions. The major components of an ESR spectrometer are a microwave source, resonance cavity, magnet, and detector.

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    Electronic nomenclature of esr and nmr

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    Spectroscopy is the experimental study of the absorption, emission, and scattering of electromagnetic radiation by atoms and molecules. There are several types of spectroscopy defined by the region of the electromagnetic spectrum used. This document focuses on electron spin resonance (ESR) spectroscopy, which involves the absorption of microwaves by unpaired electrons in a magnetic field. ESR provides information about electronic and magnetic properties as well as nuclear properties through analysis of hyperfine interactions. The major components of an ESR spectrometer are a microwave source, resonance cavity, magnet, and detector.

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    © All Rights Reserved
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    Download as pdf or txt
    68 views20 pages

    ESR and NMR

    Uploaded by

    Umang Soni
    Spectroscopy is the experimental study of the absorption, emission, and scattering of electromagnetic radiation by atoms and molecules. There are several types of spectroscopy defined by the region of the electromagnetic spectrum used. This document focuses on electron spin resonance (ESR) spectroscopy, which involves the absorption of microwaves by unpaired electrons in a magnetic field. ESR provides information about electronic and magnetic properties as well as nuclear properties through analysis of hyperfine interactions. The major components of an ESR spectrometer are a microwave source, resonance cavity, magnet, and detector.

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    Download as pdf or txt
    of 20

    Spectroscopy

    Spectroscopy is basically an experimental subject concerned


    with absorption, Emission and Scattering of electromagnetic
    radiation by atoms or molecules.
    Reference: Modern Spectroscopy – J M Hollas

    Regions of electromagnetic spectrum. Indications of region boundaries are given in


    Wavelength, frequency and wave numbers. High energy regions are indicated in electron volts.
    •ESR spectroscopy ( Frequently Microwave region)

    •NMR spectroscopy ( usually in Radiowave region)


    1. Electron Spin Resonance ( ESR)
    2. Nuclear Magnetic Resonance ( NMR)
    The major difference between electron spin
    resonance and nuclear magnetic resonance is
    that the nuclear properties are hardly affected by
    the surroundings whereas the electronic
    properties strongly dependent on the
    surroundings due to its much greater physical
    size and much smaller energy to excited states.

    ESR studies involve direct transitions between


    electronic Zeeman levels while NMR studies
    involve the direct transitions between nuclear
    Zeeman levels.
    • C.P. Poole , Electron Spin Resonance, Dover(1983), p.3
    Basic Principle of ESR

    M. Ikeya , New Appliations of Electron Spin Resonance, Word Scientific(1993),p.23


    The unpaired electrons are excited to a high energy state
    under a magnetic field by the absorption of microwave
    (music). The excited electron changes its direction of spin
    and relaxes into the ground state by emitting
    phonons(song). This absorption of electromagnetic wave (
    Microwave) is called Electron Spin Resonance ( ESR).This
    microwave absorption is measured as a function of the
    magnetic field in ESR spectroscopy.
    Wertz, John E. and Bolton, James R., Electron Spin Resonance, London,
    Chapman and Hall, 1986.
    Prob. 1
    Find the ratio of Bohr magneton to Nuclear magneton.

    Ans.
    1836

    ESR energies are generally about 2000 times as big as NMR energies.
    Prob. 2
    Calculate the ESR resonance frequency of an unpaired electron in a magnetic
    field of 0.335 T.

    Ans.
    9.3777GHz

    Prob. 3
    ESR spectrum of an unknown sample shows a single line at 0.335T at a
    frequency. DPPH (g=2.0036) show a line at 0.3375T at the same frequency.
    What is the g value corresponding to unknown sample?

    Ans.
    2.0185
    • Put sample into experimental magnetic field
    • Irradiate (microwave frequencies)
    • Measure absorbance of radiation
    • A 1st derivative spectrum is obtained from the
    unpaired electron.
    • g is a characteristic of the chemical environment of
    the unpaired electron; for free radicals it is near 2.00
    and can vary widely for transition metal centers.
    • Complicated/enhanced by hyperfine interactions with
    nuclei with non-zero spin.
    ESR Spectrometer

    •Microwave oscillator
    •Resonance cavity
    •Magnet to supply d.c. magnetic field
    •System for modulation of d.c. magnetic field
    •Detector
    •Display and Recording system
    The ESR study provides various important
    information about the system:

    1.Magnetic susceptibility of an anisotropic crystal.


    2.Information about the paramagnetic ion and its
    diamagnetic neighbours.
    3.Study of line width provides the information about
    spin-lattice and spin-spin interactions.
    4. Study of hyperfine structure provides information
    about nuclear spin, nuclear magnetic moment and
    electric quadrupole moment.
    THEORETICAL HAMILTONIAN

    The total Hamiltonian with the terms written in decreasing order of


    magnitude is
    ℋ = ℋelect + ℋ CF + ℋls + ℋss + ℋzee + ℋhf + ℋq + ℋN

    where
    ℋelect = electronic energy ( 104-105cm-1) Optical Region
    ℋ CF = crystal field energy (103-104cm-1 ) IR and optical
    ℋls = spin orbit coupling (102cm-1 )
    ℋss = spin spin interaction(0-1cm-1 )
    ℋzee = electronic Zeeman term (0-1cm-1 )
    ℋhf = hyperfine term (0-10-2cm-1)
    ℋq = quadrupole interaction (0-10-2cm-1)
    ℋN = nulear Zeeman term (0-10-3cm-1)
    Usually Zeeman and hyperfine terms are evaluated directly from
    ESR data, while the crystal field and spin-orbit energies are
    independently evaluated from Optical spectra, and are then
    correlated with the ESR data.
    Main information gained from ESR spectra is an evaluation of various terms in
    the spin Hamiltonian. ESR spectrum of a particular paramagnetic system will
    be recorded at several temperatures, several frequencies and several
    microwave powers. ESR spectrum may be employed to identify an unknown
    transition –metal ion or lattice defect, or it may distinguish between several
    valence state of the same ion. ESR spectrum frequently identifies the lattice
    site and site symmetry of the paramagnetic species, particularly in case of
    single crystals.
    Suggested reference

    Atomic and Molecular Spectroscopy


    V.K. Jain
    Narosa
    Further references:

    1. EMR/ESR/EPR spectroscopy for characterization of nanomaterials, Ashutosh Kumar Shukla (Ed.)


    A part of Springer series on Advanced Structured Materials, Vol. 62 (2017), eBook ISBN 978-81-
    322-3655-9, Hardcover ISBN 978-81-322-3653-5, Series ISSN 1869-8433
    2. Electron Spin Resonance Spectroscopy in Food Science, Ashutosh Kumar Shukla ( Ed.), Elsevier
    (2017), Paperback ISBN: 9780128054284, Published 22 December 2016
    3. Analytical Characterization of Crude Oil and Related Products, Ashutosh Kumar Shukla (Ed.),
    Wiley (2018), ISBN 9781119286318
    4. Electron Spin Resonance in Medicine, Ashutosh Kumar Shukla (Ed.), Springer(2019) Hardcover
    ISBN 978-981-13-2229-7, eBook ISBN 978-981-13-2230-3
    5. Electron Magnetic Resonance – Applications in Physical Sciences and Biology (A part of Elsevier
    series entitled Experimental Methods in Physical Sciences) (2019), Ashutosh Kumar Shukla (Ed.),
    Paperback ISBN 9780128140246, eBook ISBN: 9780128140253
    6. Medical Imaging Methods: Recent Trends, Ashutosh Kumar Shukla (Ed.), Springer (2019),
    Hardcover ISBN 978-981-13-9120-0, eBook ISBN 978-981-13-9121-7
    7. Spectroscopic tools for food quality, Ashutosh Kumar Shukla (Ed.), IOP Publishing (2020), ISBN
    0750323221, (ISBN13: 9780750323222), Published November 2019

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