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Magnetism SC L1-3
Magnetism SC L1-3
2. Text Book: T2. Huheey J. E., Keiter, Ellen A., and Keiter, Richard L., Medhi, O.K.“Inorganic Chemistry”, 4th ed., Pearson Education,
Fifth Indian Reprint 2006; T3. R. L. Dutta and A. Syamal; Elements of Magnetochemistry, 2nd Edition, EWP New Delhi, Reprint 2021.
Reference Books: R1: J. D. Lee; Concise Inorganic Chemistry, Fifth Edition, Wiley, Reprint 2021; R2: R. Sarkar; General and
Inorganic Chemistry (Part II), New Central Book Agency (P) Ltd., Reprint March 2005; Journal articles.
Magnetic moments in an
electron arises due to its Orbital
and Spin angular Momentum
For a classical rotating body: For a particle or system, γe is defined as the ratio of its
magnetic moment to its angular momentum → it is nothing
−𝒆 but a factor which converts angular momentum into
= 𝜸𝒆 = 𝒈𝒚𝒓𝒐𝒎𝒂𝒈𝒏𝒆𝒕𝒊𝒄 𝒓𝒂𝒕𝒊𝒐 magnetic moment
𝟐𝒎𝒆
An isolated electron has an angular momentum and a magnetic moment resulting from its
spin. While an electron's spin is sometimes visualized as a literal rotation about an axis, it
cannot be attributed to mass distributed identically to the charge.
The above classical relation does not hold, giving the wrong result by the absolute value of
the electron's g-factor, which is denoted ge:
−𝒆 𝒈𝒆𝝁𝑩
𝜸𝒆 = 𝒈𝒆 =
𝟐𝒎𝒆 ħ
ge = g-factor or Lande splitting factor of the free electron having value of 2.0023
Value differs appreciably for 2nd /3rd Row TMs and f-block elements
Spin-Orbit Interaction → Theoretical vs Observed Moments
Paramagnetic moment originates due to the spins and orbital motions of the unpaired electrons
in the substance → Three possible modes of coupling: spin – spin, orbital – orbital, spin – orbital
Common in lanthanides
For 1st row transition metal complexes, the orbital contribution is effectively zero and can be
ignored and then the above equation reduces to :
μeff = μspin-only = 𝟒𝑺 𝑺 + 𝟏 μb
For an ion with n number
= 𝒏 𝒏 + 𝟐 μb of unpaired electrons
Magnetic Properties (at 300 K) of some compounds of the lanthanide metals
𝟒𝝅𝒎
The number of Lines of force/cm2 at the surface of the sphere is given by =𝒎
𝟒𝝅
Intensity of Magnetization:
The intensity of magnetization (I) induced in a body by an applied magnetic field is expressed in terms of the pole strength
induced per unit area (A), i.e., I = m/A → → → This is the situation of a hypothetical monopole
When θ = 90◦
Turning moment of the couple = H → it is a measure of the work done by the magnetic field in rotating the
magnetic dipole by 90◦ i.e., from a position perpendicular to H to one parallel to H.
Properties:
• Repelled by magnetic field (closed shell electronic configuration)
• In closed shells, the spin and orbital moments of individual electrons balance each other,
leaving no net magnetic moment
• Magnetic moment induced in an external magnetic field → induced moment is proportional
to the strength of the field and will oppose the parent field.
• Independent of temperature and Permeability is less than (P<1) for diamagnetic substances
Examples: Copper, Zinc, Bismuth, Silver, Gold, Antimony, Marble, Water, Glass, Hg, alcohol, air,
H2, Ar etc.
Paramagnetism
Properties:
• Attracted in a magnetic field with a force proportional to the product of field strength and
field gradient (a variation in the magnetic field across space).
• Substances allow more lines of force to pass through it
• Under the influence of a strong magnetic field, its position is parallel to the field → aligns with
the field
• Depends on temperature (inversely proportional) and Permeability is greater than (P>1) for
paramagnetic substances
• Paramagnetic substances can be treated as a micromagnet/small bar magnet where its north
pole will face the south pole of the applied magnetic field and vice-versa.
Examples: Tungsten, Caesium, Aluminium, Manganese, alkali and alkaline earth metals (Lithium,
Magnesium, sodium), Platinum, O2 etc.
Ferro- vs Antiferro-magnetism
Magnetically Diluted System Magnetically Concentrated System
92 pm→ ←75 pm
↑42 pm
˂Fe–O–O
~115-130°
Deoxyhemoglobin
d6 : t2g4 eg2 Oxyhemoglobin (t2g6 eg0)
• Magnetic moment of Oct sites are aligned in a direction opposite to the Tet sites
• Net effect is due to the Fe(II) species only.
Superexchange
• Involves coupling of magnetic dipoles through electrons of intervening ligands
• Superexchange, or Kramers–Anderson superexchange, is the strong antiferromagnetic
coupling between two next-to-nearest neighbour cations through a non-magnetic anion. In
this way, it differs from direct exchange, in which there is coupling between nearest neighbor
cations not involving an intermediary anion.
• MnO provides a good example of superexchange (d5 system with configuration t2g3eg2)
• eg orbitals of Mn can overlap with the p-orbitals of oxygen along each of the cell axes.
- +
+ + + - - -
- +
dx2-y2 pz dx2-y2
Temperature Dependence of Paramagnetism
• Pierre Curie studied the paramagnetic molar susceptibilities of various substances at different
temperatures and obtained a general relationship (in 1895):
𝑪
χM = known as Curie’s Law
𝑻
𝑁2𝜇2 𝑁𝜇2
• T = absolute temperature; C = Curie Constant (characteristic of the substance) = =
3𝑅 3𝑘
𝑪
χM = known as Curie – Weiss Law
(𝑻−𝜽)
• T = absolute temperature; θ = Weiss Constant (unit of Temp) = a temp at which the straight line
(1/χM vs T) cuts the T-axis
Curie-Weiss Law for
Antiferromagnetic
Substance (TN)
Curie Law
𝝁𝟐
χM = N(ξ + ) where ξ = magnetizability
𝟑𝒌𝑻
𝑪
χM = A + where A = Nξ and C = N2/3k
𝑻
N𝝁𝟐
• For many practical purposes, it is convenient to neglect ξ and write: χM =
𝟑𝒌𝑻
Properties:
• Weak Paramagnetic behavior independent of T (substances may or may not have unpaired e-)
• Does not originate from any permanent magnetic dipole
• This paramagnetism is induced when the substance is placed in a magnetic field which can
affect a change in the ground state of the atom/ion
• Mixing up of higher energy excited states with the ground state and stimulation of current
through movement of e- to LUMO and (LUMO + n) orbitals (n =1, 2, 3,….)
• Also known as orbital paramagnetism where the influence of thermal agitation on their
alignment does not exist
• Systems with low-lying excited states show such TIP.
Examples: chromate (CrO4-2) and permanganate (MnO4-) ions (d0 configuration)