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 Problem
1.1 Calculate the electron density needed to produce the first crossover
in Fig. 5.21. What would the charge density have to be for the first
crossover to occur between the second and third nearest neighbors of
iron

1.2 Describe and contrast the valence electronic structure and magnetic
characteristics of i) free iron atoms
ii) atoms in metallic iron
iii) iron ions in magnetic Fe3O4

1.3 Explain what happens as copper is alloyed with nickel, Ni1-xCux.

Describe the valence electronic structure and the magnetic moment in
terms of a simple band model. Be quantitative where possible.

1.4 Calculate the effect on the total energy of an alloy as states in a flat
d-band are filled.

1.5 Verify Eqs. 5.7 and 5.9.

1.6 a) Explain why ferromagnetism is observed in nickel (4s 3d)10 but not
in titanium (4s 3d)4.
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b) Explain why ferromagnetism is observed in the metals of the 3d transition
series and not in the metals of the 3p series (e.g. Al).

1.7 You are running a billion dollar a year specialty steel operation. You
want to improve the corrosion resistance of a magnetic iron alloy but do
not want the saturation magnetization to decrease too much. While talking
in your office to an old classmate you receive a phone call that you can
buy several tons of either Mg or Ti at a bargain price. All you know is that
Mg has a positive heat of formation with iron (+20 kJ/mole) and Ti has a
negative heat of formation (-26 kJ/mole).

a) If both are equally effective in improving corrosion resistance, which

would you buy?
b) If you can justify your choice to your colleague, perhaps even
impressing him with your knowledge of the Pauli exclusion principle, he
may nominate you to be a fellow of the American Physical Society.
What do you tell him?

1.8 a) Use your understanding of the electronic structure of metals to

explain the general parabolic trend and the magnetic exceptions to that
trend shown in Figs. 5.20 a and b. While answering this question be sure to
- sketch representative electronic state densities,
- explain the relation between atomic volume and bulk modulus,
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b) Estimate the fractional volume change in Fe due to its magnetic moment
and give a numerical value for the pressure needed to cause such a
volume change. Discuss the possible relation of this effect to the structure Fe
assumes at room temperature.

1.9 a) Calculate the dipole energy of a spin 1/2 particle in the field of
another spin 1/2 particle 2 Angstroms away. Assuming they are free to
rotate, what relative alignment will they assume?
b) Calculate the coulomb energy of two point electrons 2 Angstroms apart.
c) Estimate the magnitude of the Coulomb integral

and the Exchange integral

Compare these with the magnitude of the dipole interaction energy in a)

and the electrostatic energy in b).

1.10. Ferromagnetic metals. a) Explain why ferromagnetism is observed in

nickel and not in
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aluminum.
b) Explain why ferromagnetism is observed in the second half of the 3d
transition series and not in the first half.

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 Solution
1.2 i)Free iron atoms 3d6 4s2, energy of 3d > 4s. Hund's rule applied to 3d6
results in l = 2, s = 4/2 and j = 4 so the moment is 4 mB/Fe. These moments
are independent and so behave as a paramagnet with susceptibility

ii) 3 d and 4 s states broaden into overlapping bands with 3 d74s1,

approximately, with spin up and down 3d states shifted relative to each
other. d states are broad in energy and while more spin up states are
filled, some spin down states are also filled. Moment is 2.2 mB/Fe. Sketch
band DOS

d states are narrow as fully spin split, fully spin, i.e. all spin up fill before any
spin down 3d.

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Ni has 0.6 holes in minority spin band. As Cu is added, the holes fill at a
rate of 1 electron per Cu, so the holes are gone, moment = 0, when 60%
of alloy is Cu.

1.4 The contribution of the d-band electrons to the stability of an alloy

can be expressed

which gives

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which is parabolic in the value of the Fermi energy (Fig. 5.12).

1.6 a) Early transition metals have broader d bands (lower density of states)
than do later transition metals because the sparsely-filled d orbitals of the
early transition metals see a weaker core potential than the electrons of the
later transition metals. This in itself favors moment formation in the later
transition metals based on the Stoner criterion which states that the product
of the density of states times an exchange integral (that is related to the
energy favoring parallel spins) be greater than unity. In addition, in Ni the
Fermi energy is near the top of the d band where the states are of
antibonding character; this further enhances the density of states near EF for
Ni. In Ti on the other hand, the Fermi energy is in the lower half of the d band
which is more bonding in character and thus has an even lower density of
states.
b) p orbitals are more involved in bonding (l = 1) than are d orbitals (l = 2).
Thus they are less localized and form more free-electron-like states than do d
electrons. The Stoner criterion then favors moment formation in the d series
considerably more than in the p series.

5.8 a) The band structure of the transition metals is approximately as sketched

below. The center of the d band is well below the electronic energy of the
free-atom d states (otherwise the condensed state would not be stable). Half
the d-band states are below
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and half above the center of the d band. The states near the bottom of
the d band (bonding in nature) fill first and account for the dramatic
increase in stability (depth of interatomic potential) and stiffness (related
to the curvature of the interatomic potential) and concomitant
decrease in interatomic volume in the first half of the series. The
occupation of higher-energy, antibonding states in the second half of
the series cancels the energy stabilization gained in the first half and the
trends reverse.

Magnetic moments are known to form on atoms in the 3d series metals

Cr, Mn, Fe, Co, Ni. [In the first two, these moments order
antiferromagnetically, i.e.
over a unit cell, and in the latter three, the moments order
ferromagnetically]. The exchange energy drives the establishment of an
unequal spin population in the two subbands; electrons below the Fermi
energy in one band must move to empty states above E F in the other.
Kinetic energy is measured from the bottom of the band. Hence, a

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net kinetic energy increase for the d electrons results from satisfying
Hund's rule (even partially) because more electrons now find themselves
in states farther from the bottom of the spin-up band.

Here E K is the kinetic energy of the d electrons and Z(E) and f(E) are the
density of states and the Fermi function, respectively. Just as increased
kinetic energy in a gas causes expansion, so too, in metals, moment
formation increases the kinetic energy of the d electrons causing an
increase in atomic volume.

b) This moment formation leads to a giant internal pressure. From Fig.

5.20, a volume change is seen for Fe to be of order 1 part in 7 (14%)
corresponding to a linear strain of more than 4%. The change in bulk
modulus of Fe due to its magnetic moment appears from Fig. 5.20 to be
of order 1.0 ¥ 104 kg/mm2 (100 GPa or 1.5 megabar)! 11 2

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Alternatively, using a nominal value of 1.7 ¥ 10 N/m for the bulk modulus of
Fe, the 11 magnetic stress is of order 14% ¥ 1.7 ¥ 10 = 24 GPa or 0.24
megabars.

Now it should be clearer why Fe finds itself in the BCC structure rather than
in a close-packed structure expected for a metal at room temperature. It
needs the extra atomic volume of the more open BCC structure to
accommodate this giant internal pressure.

1.9. a) If the second spin is located along the axis of the first spin, its
moment will align parallel to that of the first. If the second spin is located in
the plane perpendicular to the first, its moment will be antiparallel to that
of the first electron. In Ch. 4, we had estimated the B field seen by an
electron due to its relative motion about the nucleus (a0 = 0.52Å) to be of
order 1 T (this is the field associated with the spin-orbit interaction). For two
spin 1/2 electrons 2Å apart, the B field should be smaller than 1 T. We
cannot use the dipole field formula for the field of one spin at the position
of the other because that equation is for the far field of a dipole; closer to
a dipole the field does not vary as r -3. Instead we use the Biot-Savart law,
Eq. 1.14, and calculate the field at z = 2 Å along the axis of symmetry as
shown in the figure below.

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b) The strength of the Coulomb interaction of two electrons separated by
2 Å is e2 /(4pe0r) = 1.15 ¥ 10-18 J = 7 eV.

c) The Coulomb integral is expected to be of the same order of

magnitude as the classical Coulomb interaction, 7 eV. The probability
densities, | y 1y 1*| and | y 2y 2*|, of the two electrons drop off as exp[-
2r/a0] and exp[-2(r-2Å)/a0]. Their integration over all space represents the
net electrostatic interaction of the distributed electronic charge of the two
electrons. The Coulomb exchange integral can be estimated from the
value of the above Coulomb interaction times a factor that accounts for
the fact that the two electrons, now having parallel spins, stay on average
farther from each other; their wave functions combine in a spatially
antisymmetric way, and hence their probability density has a nodal plane
between their centers. This could be approximated by replacing the 2Å
above with a slightly larger number or by using an asymmetric wave
function on each site as illustrated below, right.
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In any case, this exchange integral is much stronger than the dipole
interaction but it is due to an entirely different mechanism, and it is not as
strong as the pure Coulomb interaction.

1.10. a) p orbitals or p bands in Al are too delocalized (essentially free

electrons), to support any moment formation which must arise from a
highly localized electronic wave function. The nearly atomic like (high
density of states) 3d wave functions of Ni allow intra-atomic exchange
(Hund's rule) to establish a moment. Interatomic exchange allows the
moment to order over long range.

b) The early transition metals have bonding valence states that are more
delocalized than those of the late transition metals which are
antibonding. The result is that the late transition metal valence states are
more highly localized and so a moment can form. They overlap enough
so that long range order can be sustained.

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