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Electron Correlations

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Prof. Dr. Narayan Prasad Adhikari

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Professor
Central Department of Physics
Tribhuvan University Kirtipur, Kathmandu, Nepal

March 13, 2024

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■Electron correlations

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• Cohesive energy: it is the energy gained by arranging the
atoms in a crystalline state, as compared with the gas
state. The strong binding of metals is represented by the

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cohesive energy which depends not only on the ions but also on
the electrons. Among several relevant energies associated with

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the e is the CORRELATION ENERGY. This energy is the
difference between the true g.s. energy and that evaluated in
the HFA and is defined by

εg = ε0 + εx + εc
(1)
OR εc = εg − ε0 − εx
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In 1, εg , ε0 and εx the g.s. energy, kinetic energy and exchange
energy respectively.

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■Electron correlations

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• It is customary to express these energies per electron in the
4
Rydberg unit which is me2h̄2
and value 13.61 eV. This energy value
also represents the Coulomb energy at a distance of twice the

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Bohr radius a0 . Kinetic Energy: We have
3 p2F
KE = ε0 = (2)

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5 2m
( )
3 1/3 −1
rs = a0 (3)
4πn
1.92 h̄2 kF2 3.68
∴ kF = =⇒ ε0F = = 2 (Ry) (4)
rs a0 2m rs
3 2.21
∴ ⟨KE⟩ = ε0F = 2 (Ry) (5)
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5 rs
• The average PE per e ⟨EP E ⟩ in the interacting system can be
estimated as;
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■Electron correlations

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e2 2
⟨P E⟩ ≃ = (Ry) (6)
rs a0 rs

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Therefore from expressions for KE and PE we get
⟨P E⟩
rs ≃ (7)

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⟨KE⟩
is a measure of the ratio of the average PE to the KE in the e gas.
• A system with rs < 1 corresponds to one with high density and
dominant KE; similarly system with rs > 1 corresponds to one
with low density and dominant PE.
• Since rs is a measure of the ratio of the Coulomb energy to the
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KE of the e gas, we may use it as a small parameter (if rs is
small) to do perturbation theory to determine the effects of
Coulomb interactions on the properties of the e gas.
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■Electron correlations

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• However, real materials typically have values of rs between 1
and 5 so that ⟨P E⟩ ≃ langleKE⟩ making the system strongly
interacting, and making it difficult to apply traditional

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perturbation theory. The importance of treating making e
effects going beyond HF will generally depend on rs and the

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dimensionality of the system under consideration.
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■Electron correlations

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For example, in 3D and rs > 100, e correlation is so strong that the e
crystallize into a crystalline arrangement forming an electronic lattice
(so called Wigner crystal.)

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• Exchange energy: The Coulomb interaction alters the g.s.
energy (KE in above expression). The first correction is the

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exchange energy εx ,

1 ∑ 4πe2
εx = ⟨0|a⃗†k+⃗qa⃗†k−⃗qa⃗k′ a⃗k |0⟩ (8)
2V ⃗ q2
k,⃗
q

where |0⟩ is the g.s. wave function,

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H0 |0⟩ = ε0 |0⟩ (9)

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Figure: Exchange diagram of electron system. k and q are ⃗k and⃗q
respectively.
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■Electron correlations

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• As shown in figure the matrix elements of εx represent two types
of configurations. The first figure is not permissible since
⃗k + ⃗q = ⃗k requires ⃗q = 0 which should be excluded. The

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exclusion is justified by considering a cloud of positive charges in
the background. The second figure yields;

since
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Ex = −

n⃗k =
1 ∑ 4πe2 ∑


1;
n⃗ n⃗
2V q⃗ q 2 ⃗ k+⃗q k

k < kF
k
(10)
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0; k > kF

we obtain

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■Electron correlations

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1 V ∫ 4πe2 ⃗
Ex = − . dkd⃗q
(2π)3 (2π)3 |⃗k+⃗q|<kF ;|⃗k|<kF q 2

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e2 kF4 (11)
= −V
4π 3

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2
3e N kF
=−
4π
as kF3 = 3π 2 n we get Exchange energy per electron as
( )
Ex 3e2 me4
Ex per e = ≡ εx = − k F = εx / Ry
N 4π 2h̄2
( ) (12)
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3 9π 1/3 1 0.916
=− =−
2π 4 rs rs
Therefore from 1
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■Electron correlations

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2.21 0.916
εc = εg − + (13)
rs2 rs

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2.21 0.916
=⇒ εg = 2 − + .... (14)
rs rs

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The g.s. energy has the appearance of a power series in increasing
powers of rs . Although it is usually unsafe to extrapolate from just
two terms, in fact εg is a series in rs . The next term will be of order
O(rs0 ). The zeroth power could be interpreted as either a constant or
as ln rs . In fact both of these terms are present. The series has the
form
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2.21 0.916
εg = 2 − − 0.094 + 0.0622 ln (rs ) + ... (15)
rs rs
∴ εc = Correlation energy = −0.094 + 0.0622 ln (rs ) + .. (16)

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The correlation energy in this form is due to Gellmann & Brueckner
Phys.Rev. 106,364(1957). If you are inetrested please apply idea of
RPA to calculate εc . This is an excellent applications of RPA.

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With more terms one gets;
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εc = −0.0937 + 0.0622 ln (rs ) + 0.086rs − 0.013rs ln (rs ) − 3 rs X3

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π
(17)
The last term is due to third and higher order exchange terms.
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• From above fig it is seen that 16 is accurate only in the limit of
rs < 1. Perturbation theory breaksdown for rs large. For real

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metals, with 2 < rs < 6, the expression for εc in 16 is not
accurate.

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• For intermediate values of rs , even thoguh there are many
formulas, the formula by Wigner gives highly accurate values as
shown. He considered the interacting e gas at very low density
i.e., rs ≫ 1. In this limit, the PE dominates KE and the
electrons condense into an e crystal in 3D at rs ≥ 100. such
wigner crystals have been observed in dilute e systems, such as e
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in a liquid He surface.

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■Electron correlations

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• To calculate the g.s. energy of the e crystal, let us divide the
crystal into Wigner-Seitz cell. From a close packed structure,
the Wigner-Seitz cell may be replaced by a sphere of volume

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4π 3
VW S ≃ r .
3 s

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• The energy per e is the energy of the e in one of the WS spheres
which consists of a KE & PE. KE comes from the zero point
motion of the e and scales like rs−3/2 which can be neglected in
the limit rs → ∞. The PE (is exchange and correlation) comes
from Coulomb interaction of the charges involved and has two
contributions;
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EP E = Ee−p + Ep−p
where Ee−p is the interaction energy between the e at the center
of the WS sphere and the poisitive neutralizing background
density
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■Electron correlations

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3
np =
4πrs3

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and it is given by
∫ ( )
3 3
Ee−p = d⃗r − =− Ry

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WS 4πrs3 rs
Similarly Ep−p is the self energy of the positive neutralizing
background charge given by
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Ep−p = Ry
5rs
Therefore
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3 6 1.8
EP E = − + =− Ry
rs 5rs rs
Since EP E = Ex + Ec and HF result of Ex = − 0.916 rs
we get
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■Electron correlations

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1.8 0.916 0.88
εc (rs ≫ 1) = − + =− Ry
rs rs rs

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Using an estimate of εc (rs ≫ 1) = −0.10 Ry from experiment,
Wigner arrived at a simple interpolation formula of
0.88
εc (rs ) = − Ry
rs + 7.9
is accurate and useful in many applications.
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■Electron-Hole droplets

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• e-hole pair can be formed by laser light illumination. Exciton =
electron + hole - its like a positronium (a positronium is a pair
of e & positron.)

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• Life time : 1µs that is 104 times greater than that of
positronium. Under certain conditions;
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Ge (exciton life time) ∼ 1 ms
Si (exciton life time) ∼ 10 µs
The life time is due to recombination or a transfer of energy to
the lattice. 16
■Electron-Hole droplets

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• (a) Excitonic Levels: Exciton is a very simple and basic
particle. Its energy structure has been revealed by spectroscopies

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studies with photon energy below the band gap, and indeed a
spectral series similar to the Rydberg series of H atom (but with
a smaller effective Rydberg energy) has been observed in Cu2 O
and other semiconductors.
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■Electron-Hole droplets

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• (b) Mobility: Exciton → highly mobile under an applied force
or due to their thermal energy. Being neutral,→ stress is used to
induce motion rather than electric field

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v
µ= (18)
F
drift momentum: mv = F τ. τ is scattering time and m is

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exciton mass.
v
τ = m = mµ (19)
F
Therefore drift velocity determines the scattering time. Tamor
and Wolfe determined the exciton velocity and found that the
data can be fitted to
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τ = 8.8 × 10−10 T −3/2 (20)
The temperature dependence is due to acoustic phonon
scattering model.
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■Electron-Hole droplets

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At 13 K; eτ
m
= 4 × 106 cm2 /V − s; ∴ D = τ kBmT = 300T −1/2 cm2 /s
Therefore at T=11 K;D = 90cm2 /s confirmed by an independent
experiment.

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• (c) Bose-Einstein Condensation:The condensation
temperature in ideal Bose gas is;
( )3/2

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2πmkB T
n = 2.612 (21)
h2
Therefore for BEC n has to be high as
n2/3
T ∝ (22)
m
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and m is quite low for e-hole pair, the transition temperature is
expected to be much higher than in liquid He.
• excito gas improtant from the point of BEC for example;
excitons in Cu2 O =⇒ repulsive interactions among the
excitons. Hence Low effective19mass. Therefore higher Tc .
■Electron-Hole droplets

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• Further it is conceivable that excitons mediate
superconductivity as phonons do for the ordinary SC.

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■Electron-Hole droplets

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Hole mass in Cu2 O =⇒ 0.7m0
• Exchange interactions splits the n = 1 level of the so-called

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yellow series into a triply degenerate orthoexciton (An exciton
whose spin is parallel to that of its hole) and a singly degenrate
paraexciton. The paraexcitons have a rather long life time of

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around 10µs at 15 K.Such a long life time is an additional
advantage for observing BEC. Time resolved spectral and spatial
measurements of photoluminescence in Cu2 O at low
temperature show that the gas density follows the expected T 3/2
variation of the ideal Bose gas. Moreover, the paraexcitons are
found to undergo BEC at high densities.
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• interested can see: Snoke et al. PRL 64,2543(1990)

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■Electron-Hole droplets

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• (d) Bohr Radius:The interaction potential between the
electrons and holes is Coulombic, but its magnitude is reduced
considerably by the dielectric constant of the medium.

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Ge(εr ) = 15.4; Si(εr ) = 11.4; GaAs(εr ) = 12.35;

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The effective Bohr radius is;
κh̄2
a∗0 = (23)
µ0 e 2
where µ0 , the reduced mass is defined by
1 1 1
= + (24)
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µ0 me mh
a∗0 : Ge → 177; Si → 49; GaAs → 140; ∴ BE ∼
(0.01 − 0.001)of H atom.
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■Electron-Hole droplets

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• (e) Metal-Insulator Transition: As the density of sxcitos
increases, the excitons may be ionized so that the system
becomes metallic. While this transition has been treated in

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several ways, the Mott criterion based on a consideration of
screening is simple. In the metallic state, the Coulomb potential

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between an e & a hole is screened by nearby charges in the
form;
e2 r
ϕ(r) = − exp (− ) (25)
κr rT F
where κ is the dielectric constant of the system. Near absolute
zero, the screening constant is given by the Thomas-Fermi
screening length rT F defined by
PA
( )1/2 ( )1/6
κ π
rT F = h̄ (26)
8me e2 3n

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■Electron-Hole droplets

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The screening constant is given by the Debye length;
( )1/2
κkB T
rD = (27)
8πne2

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Here the Denominator factor is 8 instead of 4 because the system has

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two components.
• The potential ϕ(r) is the long range attractive coulomb
potential for very small carrier density n. Hence, a pair of free
carriers may not exist.However, if the carrier density is increased,
the screening due to nearby charges will become more and more
effective. The critical density may be obtained from the
Schrödinger problem for a pair of particles with the above
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Coulomb potential such that the binding energy falls to zero. It
is found that at this density the screening length is close to the
exciton Bohr radius
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■Electron-Hole droplets

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rT F (nc ) = 0.84aex (28)

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At this point, the metallic plasma will become a neutral exciton gas.
That is a metal-insulator (Mott) transition has taken place.
you can develop more on Mott transition from his paer or other
standard texts ....
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■Electron-Hole droplets

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• (f) Electron-hole Liquid: The exciton can condense into a
liquid state in the form of droplets when their density exceeds a

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critical value. Such a condensation, which was first predicted by
Keldysh in 1968, has indeed been observed. Rayleigh scattering

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has shown liquid droplets of about 2µm in size.

• These droplets consist of ≃ 107 e-hole pairs and are massive so

that they are expected to move only slowly. some basic aspects
of
• Let us describe some basic aspects of the exciton luminescence
in connection with the e-hole liquid (ehl) formation. insert a
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figure intensity of luminescence vs photon energy

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■Electron-Hole droplets

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■Electron-Hole droplets

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• When the density of excitons is small, a sharp luminescence line

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is observed (see figure above)
• The top two curves represent this. At lower temp. two peaks

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appeared Ex 2 → exciton molecules and Ex → free excitons
• finally at 1.4 K a broad line representing ehl was observed. That
is both of these excitons condensed into an ehl with density
3.3X1018 cm−3 .

• The free exciton line is due to recombination of free e and holes.

Figure below shows Schematic energy diagram
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■Electron-Hole droplets

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■Electron-Hole droplets

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• The two parabolic curves represent the conduction band and
valence bands with a separation of ε′gap which is renormalized

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from the band gap εgap due to the presence of other interacting
electrons and holes. These bands are filled to their respective

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Fermi levels.
• An e with energy εe and a hole with energy εh recombine,
transfer energy h̄ωph to the lattice and emit a photon of energy
hν. The condensate chemical potential is given by

µ = ε′gap + εF where εF = εF e + εF h (29)

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■Electron-Hole droplets

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• At low density and high temperature, excitons are in a gas phase
and are neutral. As their density increases, a first order phase
transition into a metallic liquid state takes place below a critical

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temperature. Figure shows experimental phase diagram

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■Electron-Hole droplets

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• The free exciton gas coexists with liquid droplets a t around 15
K in temperature and 1017 cm−3 in density. The crosses in figure
represents metal-insulator transition.

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• High density side; ehl density ∼ T 2 with n0 = 3.3X1018 cm−3 at
0 K. In the classical regime, the Mott criterion states

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kB T
nM (T ) = (30)
16πεex a30
a0 = Bohr radius = 44
εex = binding energy =14.7 meV At T= 0 K;
nM (0) = 1.3X1014 cm−3 .
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nM (T ) = 1.5X1015 T (31)
The critical temperature Tc = 27 ± 1K. and
nc ∼ 1.1X1018 cm−3 .
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■Electron-Hole droplets

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The limiting density at 0 K is n0 = 3.3X1018 cm−3 . The phase
diagram can be obtained by free energy expansion. Condition for
formation of e-hole pairs

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The energy of N e-hole pairs in a volume V can be expressed as;

E = N ε(n) + N ε′gap (32)

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ε′gap being the effective energy gap between the valence and
conduction bands, which includes the correction due to the
correlations of the particles. The width of the liquid-line depends on
the momenta of e and holes which range from zero to the maximum
corresponding to their chemical potential or the actual Fermi energy.
PA
The upper edge, that is, the violet boundary of the liquid line is given
by
h̄ωv = ε′gap + µL (33)

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■Electron-Hole droplets

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where µL is the chemical potential of the liquid measured from the
gap edge ε′gap . It is the sum of the actual Fermi energies of the
electrons and holes and is equal to

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N +1 N ∂ε
µL = (N + 1)ε( ) − N + ε( ) = ε(n) + n (34)
V V ∂n

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At equilibrium density n0 , the derivative vanishes:
( )
∂ε
(35)
∂n n0

Hence in equilibrium;
PA
µL = ε(n0 )
The low frequency edge, that is the red boundary, of the liquid line is
essentially determined by the band gap.
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■Electron-Hole droplets

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However, this energy must be renormalized in consideration of the
effects of collective interactions. This renormalized band gap ε′gap is

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given by
h̄ωr = ε′gap = εgap + ε(n0 ) − (εF e + εF h ) (36)
The difference between 33 and 36 is;
PA

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■Electron-Hole droplets

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h̄(ωv − ωr ) = εF e + εF h (37)

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The equilibrium density of droplets at absolute zero corresponds to
the minimum of function ε(n). Condensation takes place when the
minimum energy per particle, ε(n0 ), is lower than the excitonic
binding energy εexc :
ε(n0 ) < εexc (38)
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■Heavy Fermions

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• The fermions having effective mass higher than the bare mass
are called ”Heavy Fermions”. For example; U P t3 follows;
C

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= γ + βT 2 + δT 2 ln (T ) (39)
T
where γ, β & δ are constants. The 2nd term on the RHS

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represents lattice contributions. In another type;
C
∼ T −1.6 OR T −0.88 − T −1.8 (40)
T
and in yet another type we get
C
≃γ (41)
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T
C
So in Heavy fermions the ratio T
follows in general three
different rules 39, 40 and 41.
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■Heavy Fermions

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• The heavy fermions which follow 41 are ”Type I Heavy
Fermions”, those which follow 40 are ”Type II Heavy Fermions”
and those which follow 39 are ”Type III Heavy Fermions”. Main

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example of Type II is CeCu2 follows first one power law -1.6
whereas CeCu6/CeAl3 follw power law -0.88 to -1.8.

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• The Kondo effects is due to the interactions between the
conduction e and localized magnetic moments of magnetic
impurities. These impurities are usually dilute and cause spin-flip
scattering. The χ follows the Curie-Weiss law at high
temperatures due to the localized magnetic moments and
PA
becomes constant below a certain temperature characteristic of
a metal when the magnetic moments are shielded by conduction
e.

39
■Heavy Fermions

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• Two distinctive phenomena take place as the concentration of

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magnetic impurities increases.
• 1. No Kondo effects in transition elements due to overlapping of

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d orbitals as size of d orbitals is wide. Consequently ”spin glass”
state occurs.
• 2. In the case of rare-earth atoms such as cerium or yetterbium
with very localized f orbitals, the overlapping of the f-orbitals
may not take place. Hence, the rare-earth impurities form a
Kondo lattice. In such a lattice each impurity atom scatters
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conduction e as in the dilute case.

40
■Heavy Fermions

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■Heavy Fermions

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■Heavy Fermions

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■Heavy Fermions

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• From the figure of χ vs T, we see that at relatively high
temperatures, the χ ∼ T1 in CeCu6, CeAl3 and CeCu2Si2.
• From the figure of ρ vs T, we see that ρ increases logarithmically

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as temperature decreases. Therefore they form Kondo lattices.
• However, in CeG6 or CePb3 magnetic ordering destroys the

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kondo effects.
• In general the lower the Kondo temp., the higher the χ. This
provides one possible mechanism for the appearance of a large
effective mass.
• the relative resistivity of CexLa1-xCu6 is shown in another figure
PA
above In the figure, the ordinate represents
ρx − ρ0
ρm =
x
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■Heavy Fermions

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where the suffix ”x” represents the concentration of cerium atoms.
• At around 50 k, the resistivity increases toward low
temperatures. However, when the concentration is above 80%,

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the resistivity drops after it attends its maxima. The kondo
temp at x=0.094 is estimated to be 3.7 K. The residual

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resistivity per mole of cerium varies as

320x(1 − x) (42)
• The spin-spin correlation between the cerium atoms is varied by
Lanthanum atoms.
• While actual heavy fermion systems show differences in their
PA
properties, the disappearance of a magnetic moment is
common.Theoretically, transition from a magnetic to
nonmagnetic state can be expected to be due to energy gain.
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■Heavy Fermions

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• Therefore, let us try to find whether or not such an energy gain
is possible based on the simplest model in which a single
magnetic ion is placed in a Fermi liquid of conduction electrons.

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A similar model has been discussed for the Kondo effects.
• A single ion with an f orbital can be treated in terms of the

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Anderson Hamiltonian ;
• εf & H0 (with suffix ’f’ for f orbital) can be separated. Hence
the coupling between the f and conduction e may be assumed to
depend only on the magnitude of the k-vector and is
characterized by a constant interaction amplitude V. The
number operator of the f electrons in the mth state is denoted
PA
†
by nfm = fm fm where 1 ≤ m ≤ νf = (2J + 1), which represents
the degeneracy of the f orbital. As a consequence, we obtain a
Hamiltonian
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■Heavy Fermions

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∑ ∑
H = H0 + ε(k)c†kσ ckσ + εf nfm
k,σ m
∑ ∑
(43)
U

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† †
+ nfm nfm1 +V (fm ckm + ckm fm )
2 m,m1;m̸=m1 k,m

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We are concerned with two types of spin states, spin zero singlet
states and magnetic multiplet states. The energies associated with
these two states are represented by εs and εm respectively, and their
difference by ε;
εs = εm + ε (44)
The energy εm can be expressed as
PA
εm = ε0 + εf (45)
where ε0 is the g.s. energy corresponding to |ϕ0 ⟩ which is completely
filled Fermi sea.
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■Heavy Fermions

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• A trial wave function for the singlet state is constructed by
alinear combination of the g.s. and the states
†
fm ckm |ϕ0 ⟩

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in which asingle conduction e is transfered to the localized state
m. This linear combination is expressed as;

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[ ]
∑
†
|Ψ⟩ = a 1 + b(k)fm ckm |ϕ0 ⟩ (46)
k
The energy of this state is;
⟨Ψ|H|Ψ⟩
εs = (47)
⟨Ψ|Ψ⟩
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The magnetic multiplet state will be represented by |Ψm ⟩;
†
|Ψ⟩ = fm |ϕ0 (48)

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■Heavy Fermions

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• This state has an additional e. The energy εs is determined
thro’ variations w.r.t. nf and also to the hybrid parameter b(k).
The stationary conditions are;
√ ∑

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ε = −εf + V νf b(k) (49)
k
√

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εb(k) = V νf − ε(k)b(k) (50)
Solving above two equations we get;
∑ 1
ε = −εf + νf V 2 (51)
k ε + ε(k)
The solution of 51 can be obtained by plotting both sides
against ε. We find then for small V that there is a solution ε
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that is negative. This means, the system can gain energy by
entering the singlet state, which is nonmagnetic. The
normalization constant a of the singlet state can be expressed in
terms of the f-level occupancy49 nf such that
■Heavy Fermions

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|a|2 = 1 − nf (52)
when a magnetic field is applied, the energy εf becomes

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εf − gµB mH, with m varying between -J and J. The k sum in the
above eq will be changed in such a way that

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∑ ∑
νf → (53)
k k,m

• Otherwise the corresponding energy is given in a similar form.

The magnetic susceptibility can then be obtained by the second
derivative of the energy in the following form:
PA
J(J + 1) 1 n2f
χ = (gj µB )2 (54)
3 νf Γ 1 − n f
where
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■Heavy Fermions

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Γ = πg(εF )V 2 (55)

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with g(εF ) is density of states per spin of the conduction e on the
Fermi surface.

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• The specific constant (γ) in above equation 39 can be shown to
be inversely proportional to |ε|. Reexpressing this quantity, we
find that γ is given by;

π2 2 1 n2f
γ= kB (56)
3 νf Γ 1 − nf
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Eq 54 and 56 both show that χ and γ increase as nf
approaches 1.

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■Heavy Fermions

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• Note: Above results are over simplified. In actual heavy

CM
fermion systems, the ions form a crystal, and a certain
consideration of their magnetic interactions is necessary
(out of scope of this lecture. however any interested can
go thro’ Advances in SSP.)
PA

52
■Heavy Fermions

II
• Some heavy fermion systems become superconductors in spie of
their large effective masses

P
CeCu2 Si2 → Tc = 0.7K
→ Tc

CM
U Be13 = 0.9K
U P t3 → Tc = 0.5K
U Ru2 Si2 → Tc = 1.5K

• The temperature variations of the specific heat is anomalous at

PA
the SC transition point, and the ratio C/T reaches a peak.
BCS Theory→ ∆C γTc
= 1.43 where ∆C is the jump at Tc.

53
■Heavy Fermions

II
∆C
In CeCu2 Si2 → = 1.2
γTc

P
∆C
In U Be13 → = 2.5
γTc

CM
∆C
In U P t3 → = 0.6
γTc

Below Tc, the specific heat capacity of heavy fermion system does not
decrease exponentially following exp (− kB∆T ) rather it is as follows;
In CeCu2 Si2 → C ≃ T 2.4
PA
In U Be13 → C ≃ T 2.9
In U P t3 → C ≃ T 2
54
■Heavy Fermions

II
• The ultrasonic attenuation coefficient α in the BCS type SC
decreases sharply below Tc and their NMR relaxation time T1
increases toward a maximum just below Tc and then decreases

P
to zero. On the other hand, the attenuation coefficient in UPt3
and UBe13 decreases slowly in proportional to T 2 . Also, T1 of

CM
both CeCu2Si2 and UBe13 does not increase below Tc but
decreases in proportional to T 3 .

• Therefore, these heavy fermions do not seem to become s-wave

BCS SC. Instead they can be p-wave SC. The case of CeCu2Si2
appears to be in a spin singlet state with an anisotropic energy
PA
gap that may vanish in a certain direction. When impurities are
added to expand the lattice, this material favors anti-FM
ordering.

55
■Heavy Fermions

II
• Let us try to understand the relation between such as AFM spin
configuration and SC based on strong couplingg limit of the
Hubbard hamiltonian;
∑ ( ) ∑

P
H=t ij a†iσ ajσ + a†jσ aiσ + U ni↑ ni↓ (57)
i

CM
For U → large, 57 reduces to an antiferromagnetic Heisenberg
model in a band that is half-filled. Each site in this case has one
e. From this limit, the hopping term is considered to cause
perturbation.
• to first order in t the KE may be expected to have the form;
∑ ( )
H1 = t ij c†iσ cjσ + c†jσ ciσ (58)
PA
Here the new operators ciσ hop single e from site to site. In
contrast to aiσ they are not true fermion operators since they do
not allow double occupancy.
56
■Heavy Fermions

II
This means
ci↑ c†i↓ = 0 (59)

P
• These operators decide spinless fermions in one D. their role is
unknown in higher dimension. We assume that the system is

CM
still describable by spinless fermions.
• Perturbaion to first order in (t/U) allows virtual transitions into
states with doubly occupied sites. The effective hamiltonian that
acts only on the states with singly occupied sites can be
expected to be characterized by energy that is proportional to
t(t/U) :
( )
t2
PA
1
Vij = 2 σi σj − (60)
U 4
This interaction energy corresponds to superexchange between
NN spins.
57
■Heavy Fermions

II
• Superexchange Interaction: superexchange or
Kramers-Anderson superexchange is the strong (usually)
antiferromagnetic coupling between two NN cations through a

P
nonmagnetic anion. In this way, it differs from direct exchange
in which there is coupling between NN cations not involving an

CM
intermediary anion.
PA

Figure: Mn atoms interact with one another despite having nonmagnetic

O atom between them.
58
■Heavy Fermions

II
P
• Superexchange is a result of the electrons having come from the

CM
same donor atom and being coupled with the receiving ions
spins. If the two next-to-nearest neighbors, positive ions are
connected at 900 to the bridging non-magnetic anion, then the
interaction can be a ferromagnetic interaction.
PA

59
■Heavy Fermions

II
• Quantum mechanical perturbation theory results in an AFM
interaction of the spins of neighboring Mn atoms with the
energy operator;

P
2t2
H1,2 = M n,O ⃗σ1 .⃗σ2 (61)
U

CM
where tM n, O is the so-called hopping energy between a Mn-3d
and Oxygen-p orbitals. ⃗σ1 and ⃗σ2 are Mn spin vector operators.
• The interaction energy 60 corresponds to superexchange
between NN spins. It is antiferromagnetic in that antiparallel
2
spin pairs have lower energies by ( 2tU ).
PA
• If two electrons with opposite spins are favored in NN sites, they
will have an effective attraction, which can be a cause of
Superconductivity.

60
■Heavy Fermions

II
• A similar attraction results from the Anderson lattice model with
d and f electron sites:
∑ ∑
(d†iσ djσ +d†jσ diσ )+V (d†iσ fiσ +fiσ
†

P
H =t diσ )
ij,σ
∑ ∑
i,σ
∑ (62)

CM
+ εd ndiσ + εf nf iσ + U nf i↑ nf i↓
i,σ i,σ i

perturbation to lowest order in V (εd − εf ) reveals that the

energy of the singlet state for U → ∞ is lowered from the case
U=0 by the Kondo coupling characterized by
2V 2
∆E = (63)
PA
(εd − εf )
Thus, the mechanism for lowering energy is somewhat different
from the earlier case.
61