After a review of quantum mechanics and atomic physics, the binding energy and electronic energy levels in

molecules and solids are discussed. The free-electron theory of metals is introduced and applied to the
quantitative treatment of a number of electron emission effects. The band theory of solids is developed
quantitatively via the Kronig-Penney model, and the transport properties of metals and semiconductors are
discussed in detail. The physical principle of pn junctions, transistors, tunnel diodes, etc. is explained.
Fundamentals and applications of photoconductors, lasers, magnetic materials, and superconductors are
also discussed. (ESG 332 is not a prerequisite.)

Quantum mechanics is the branch of science that explore the behavior of matter at extremely
small scale. Quantum mechanics run counter to classical mechanics where matter of a larger
scale behave as expected in day to day interactions. and the wacky behavior of photons, electrons
and the other particles that make up the universe.

Quantum mechanics is the branch of physics relating to the very small.

It results in what may appear to be some very strange conclusions about the physical
world. At the scale of atoms and electrons, many of the equations of classical mechanics,
which describe how things move at everyday sizes and speeds, cease to be useful. In
classical mechanics, objects exist in a specific place at a specific time. However, in quantum
mechanics, objects instead exist in a haze of probability; they have a certain chance of being
at point A, another chance of being at point B and so on.
Three revolutionary principles
Quantum mechanics (QM) developed over many decades, beginning as a set of
controversial mathematical explanations of experiments that the math of classical
mechanics could not explain. It began at the turn of the 20th century, around the same time
that Albert Einstein published his theory of relativity, a separate mathematical revolution
in physics that describes the motion of things at high speeds. Unlike relativity, however, the
origins of QM cannot be attributed to any one scientist. Rather, multiple scientists
contributed to a foundation of three revolutionary principles that gradually gained
acceptance and experimental verification between 1900 and 1930. They are:
Quantized properties: Certain properties, such as position, speed and color, can
sometimes only occur in specific, set amounts, much like a dial that "clicks" from number to
number. This challenged a fundamental assumption of classical mechanics, which said that
such properties should exist on a smooth, continuous spectrum. To describe the idea that
some properties "clicked" like a dial with specific settings, scientists coined the word
"quantized."
Particles of light: Light can sometimes behave as a particle. This was initially met with
harsh criticism, as it ran contrary to 200 years of experiments showing that light behaved
as a wave; much like ripples on the surface of a calm lake. Light behaves similarly in that it
bounces off walls and bends around corners, and that the crests and troughs of the wave
can add up or cancel out. Added wave crests result in brighter light, while waves that cancel
out produce darkness. A light source can be thought of as a ball on a stick
being rhythmically dipped in the center of a lake. The color emitted corresponds to the
distance between the crests, which is determined by the speed of the ball's rhythm.
Waves of matter: Matter can also behave as a wave. This ran counter to the roughly 30
years of experiments showing that matter (such as electrons) exists as particles.

Quantized properties?
In 1900, German physicist Max Planck sought to explain the distribution of colors emitted
over the spectrum in the glow of red-hot and white-hot objects, such as light-bulb
filaments. When making physical sense of the equation he had derived to describe this
distribution, Planck realized it implied that combinations of only certain colors (albeit a
great number of them) were emitted, specifically those that were whole-number multiples
of some base value. Somehow, colors were quantized! This was unexpected because light
was understood to act as a wave, meaning that values of color should be a continuous
spectrum. What could be forbidding atoms from producing the colors between these
whole-number multiples? This seemed so strange that Planck regarded quantization as
nothing more than a mathematical trick. According to Helge Kragh in his 2000 article in
Physics World magazine, "Max Planck, the Reluctant Revolutionary," "If a revolution
occurred in physics in December 1900, nobody seemed to notice it. Planck was no
exception …"

Planck's equation also contained a number that would later become very important to
future development of QM; today, it's known as "Planck's Constant."

Quantization helped to explain other mysteries of physics. In 1907, Einstein used Planck's
hypothesis of quantization to explain why the temperature of a solid changed by different
amounts if you put the same amount of heat into the material but changed the starting
temperature.
Since the early 1800s, the science of spectroscopy had shown that different elements emit
and absorb specific colors of light called "spectral lines." Though spectroscopy was a
reliable method for determining the elements contained in objects such as distant stars,
scientists were puzzled about why each element gave off those specific lines in the first
place. In 1888, Johannes Rydberg derived an equation that described the spectral lines
emitted by hydrogen, though nobody could explain why the equation worked. This changed
in 1913 when Niels Bohr applied Planck's hypothesis of quantization to Ernest
Rutherford's 1911 "planetary" model of the atom, which postulated that electrons orbited
the nucleus the same way that planets orbit the sun. According to Physics 2000 (a site from
the University of Colorado), Bohr proposed that electrons were restricted to "special"
orbits around an atom's nucleus. They could "jump" between special orbits, and the energy
produced by the jump caused specific colors of light, observed as spectral lines. Though
quantized properties were invented as but a mere mathematical trick, they explained so
much that they became the founding principle of QM.
Particles of light?
In 1905, Einstein published a paper, "Concerning an Heuristic Point of View Toward the
Emission and Transformation of Light," in which he envisioned light traveling not as a
wave, but as some manner of "energy quanta." This packet of energy, Einstein suggested,
could "be absorbed or generated only as a whole," specifically when an atom "jumps"
between quantized vibration rates. This would also apply, as would be shown a few years
later, when an electron "jumps" between quantized orbits. Under this model, Einstein's
"energy quanta" contained the energy difference of the jump; when divided by Planck’s
constant, that energy difference determined the color of light carried by those quanta.
With this new way to envision light, Einstein offered insights into the behavior of nine
different phenomena, including the specific colors that Planck described being emitted
from a light-bulb filament. It also explained how certain colors of light could eject electrons
off metal surfaces, a phenomenon known as the "photoelectric effect." However, Einstein
wasn't wholly justified in taking this leap, said Stephen Klassen, an associate professor of
physics at the University of Winnipeg. In a 2008 paper, "The Photoelectric Effect:
Rehabilitating the Story for the Physics Classroom," Klassen states that Einstein's energy
quanta aren't necessary for explaining all of those nine phenomena. Certain mathematical
treatments of light as a wave are still capable of describing both the specific colors that
Planck described being emitted from a light-bulb filament and the photoelectric effect.
Indeed, in Einstein's controversial winning of the 1921 Nobel Prize, the Nobel committee
only acknowledged "his discovery of the law of the photoelectric effect," which specifically
did not rely on the notion of energy quanta.
Roughly two decades after Einstein's paper, the term "photon" was popularized for
describing energy quanta, thanks to the 1923 work of Arthur Compton, who showed that
light scattered by an electron beam changed in color. This showed that particles of light
(photons) were indeed colliding with particles of matter (electrons), thus confirming
Einstein's hypothesis. By now, it was clear that light could behave both as a wave and a
particle, placing light's "wave-particle duality" into the foundation of QM.
Waves of matter?
Since the discovery of the electron in 1896, evidence that all matter existed in the form of
particles was slowly building. Still, the demonstration of light's wave-particle duality made
scientists question whether matter was limited to acting only as particles. Perhaps wave-
particle duality could ring true for matter as well? The first scientist to make substantial
headway with this reasoning was a French physicist named Louis de Broglie. In 1924, de
Broglie used the equations of Einstein's theory of special relativity to show that particles
can exhibit wave-like characteristics, and that waves can exhibit particle-like
characteristics. Then in 1925, two scientists, working independently and using separate
lines of mathematical thinking, applied de Broglie's reasoning to explain how electrons
whizzed around in atoms (a phenomenon that was unexplainable using the equations
of classical mechanics). In Germany, physicist Werner Heisenberg (teaming with Max Born
and Pascual Jordan) accomplished this by developing "matrix mechanics." Austrian
physicist Erwin Schrödinger developed a similar theory called "wave mechanics."
Schrödinger showed in 1926 that these two approaches were equivalent (though Swiss
physicist Wolfgang Pauli sent an unpublished result to Jordan showing that matrix
mechanics was more complete).
The Heisenberg-Schrödinger model of the atom, in which each electron acts as a wave
(sometimes referred to as a "cloud") around the nucleus of an atom replaced the
Rutherford-Bohr model. One stipulation of the new model was that the ends of the wave
that forms an electron must meet. In "Quantum Mechanics in Chemistry, 3rd Ed." (W.A.
Benjamin, 1981), Melvin Hanna writes, "The imposition of the boundary conditions has
restricted the energy to discrete values." A consequence of this stipulation is that only
whole numbers of crests and troughs are allowed, which explains why some properties are
quantized. In the Heisenberg-Schrödinger model of the atom, electrons obey a "wave
function" and occupy "orbitals" rather than orbits. Unlike the circular orbits of the
Rutherford-Bohr model, atomic orbitals have a variety of shapes ranging from spheres to
dumbbells to daisies.
In 1927, Walter Heitler and Fritz London further developed wave mechanics to show how
atomic orbitals could combine to form molecular orbitals, effectively showing why atoms
bond to one another to form molecules. This was yet another problem that had been
unsolvable using the math of classical mechanics. These insights gave rise to the field of
"quantum chemistry."
The uncertainty principle
Also in 1927, Heisenberg made another major contribution to quantum physics. He
reasoned that since matter acts as waves, some properties, such as an electron's position
and speed, are "complementary," meaning there's a limit (related to Planck's constant) to
how well the precision of each property can be known. Under what would come to be
called "Heisenberg's uncertainty principle," it was reasoned that the more precisely an
electron's position is known, the less precisely its speed can be known, and vice versa. This
uncertainty principle applies to everyday-size objects as well, but is not noticeable because
the lack of precision is extraordinarily tiny. According to Dave Slaven of Morningside
College (Sioux City, IA), if a baseball's speed is known to within a precision of 0.1 mph, the
maximum precision to which it is possible to know the ball's position is
0.000000000000000000000000000008 millimeters.
Onward
The principles of quantization, wave-particle duality and the uncertainty principle ushered
in a new era for QM. In 1927, Paul Dirac applied a quantum understanding of electric and
magnetic fields to give rise to the study of "quantum field theory" (QFT), which treated
particles (such as photons and electrons) as excited states of an underlying physical field.
Work in QFT continued for a decade until scientists hit a roadblock: Many equations in QFT
stopped making physical sense because they produced results of infinity. After a decade of
stagnation, Hans Bethe made a breakthrough in 1947 using a technique called
"renormalization." Here, Bethe realized that all infinite results related to two phenomena
(specifically "electron self-energy" and "vacuum polarization") such that the observed
values of electron mass and electron charge could be used to make all the infinities
disappear.

The notion of an “effective model” or “effective potential” pervades essentially all of

physics. Even at the undergraduate level, for example, it is worth emphasizing that the
lowly harmonic oscillator potential is really merely an “effective potential”. In reality all
potentials are generally more complicated—the spring will eventually stretch
inelastically—and any potential has a useful domain of applicability in every problem.

One can go further with “effective models”, with perhaps the best-known example
being Feynman’s description of the ammonia molecule as a two-state system1. This sort
of description is worthwhile for certain aspects of the problem, such as the time
dependence of the wave function, but it often remains unclear how parameters required
in the effective model are related to underlying “microscopic” characteristics of the
same problem. A more concrete realization of the Feynman two-state system is the
double-well potential. In ref.2 (see also ref.3) the states describing a particle in such a
system were determined from the basic parameters, namely the barrier height and
width. At the same time, a “toy model” describing a two-state system with a single
parameter, a transition amplitude t, to describe tunneling through the barrier
(analogous to the amplitude for the nitrogen atom to tunnel from below to above the
plane of hydrogen atoms in the ammonia example), was shown to very accurately
describe the ground state splitting calculated by solving the complete Schrödinger
equation. This was an example of a case where the original model, with a Hilbert space
consisting of an infinite number of states was approximately mapped onto a “toy” or
“effective” model consisting of just two states.

In this paper we want to focus on a natural extension of this model, which occurs often
in condensed matter, and leads to a “starting” model for studying strongly correlated
electron systems. In this case we start with a periodic array of some potential that gives
rise to energy bands, whose characteristics require a complete solution to the
Schrödinger equation. This calculation in principle involves an infinite Hilbert space, in
two senses. First, even a single potential well, representing a single atom with which an
electron interacts, requires an infinite Hilbert space. However, for a solid there are a
large number of these wells—an infinite number if we allow the solid to go on forever.
This latter infinity is handled analytically through Bloch’s theorem4,5,6,7, which allows
solution of the electron wave function in the infinite periodic array in terms of the
solution within a single unit cell (see also ref.8 where some context for this theorem is
provided). Even with Bloch’s theorem, however, an infinite Hilbert space is required to
describe the (infinite) set of energy bands that emerges from the periodicity. An
effective model, known as a tight-binding model, reduces the infinite Hilbert space
down to an N-dimensional Hilbert space, where N is the number of atoms. This
description is entirely analogous to the reduction of the double-well potential to a 2-
dimensional Hilbert space, involving a single tunneling parameter t, and in fact, even
as N  →  ∞, only a single parameter t, called the “tunneling amplitude”, remains.

This “down-folding” process is often carried out for complete descriptions of rather
complicated systems, often with approximations or parameterizations along the way9.
The purpose of this paper is to implement this procedure using the simplest model
possible, i.e. the one-dimensional Kronig-Penney model10. The result is a derivation of
the one or two parameters in the “effective” tight-binding model, in terms of the
microscopic parameters that describe the original Kronig-Penney model. This
calculation is possible because some aspects of the one-dimensional Kronig-Penney
model are known analytically.

For reasons that will become clear as we proceed, comparisons are required with the
double-well case (i.e. a Kronig-Penney model with only 2 cells). This solution,
performed for a configuration pertinent to the infinite-cell Kronig-Penney model, is
described in Appendix A. Our numerical solutions confirm that this description is exact
in the limit of tightly-bound wells, and we explore further to what degree this
description remains accurate as the coupling between wells increases. Remarkably, we
find that the need for so-called next-nearest-neighbour (nnn) hopping does not
necessarily imply next-nearest-neighbour hopping. This exercise, carried out here only
for this specific model10, gives us a deeper understanding of the connection between
effective models and their more microscopic counterparts.

These results complement the phenomenological fits realized in refs2,7. The first
reference describes a double-well potential, and can be thought of as a special
preliminary case of the fully periodic solid. This form of the double-well potential
treated in this reference is not directly applicable to the present problem but, for
completeness, we include its solution separately in Appendix B.

Kronig-Penney Model
The one-dimensional Kronig-Penney model10 consists of an electron moving in a
periodic potential as depicted in Fig. 1, with alternating wells of width w and barriers of
width b and height V 0. The basic building block of this model is the unit cell, here
consisting of one well surrounded by two (half) barriers; in the limit that the barrier
heights and/or widths become large, a good starting point for this problem is the
solution to the problem of a single well, and we will exploit this in what follows.
However, the physics that emerges from the Kronig-Penney model is already contained
in the double-well potential, whose solution is given in Appendix A (see also Appendix
B for the solution to the double-well considered in ref.2),

Figure 1

A pictorial representation of the periodic potential in the Kronig-Penney model, illustrating

wells of depth V 0 and width w separated from one another by barriers of width b.
Full size image
Proceeding with the Kronig-Penney model, the analytical solution for the energy levels
(E  <  V 0) is well known; the implicit equation for the energy is

cos(𝑘ℓ)=cos(𝑘𝑘)cosh(𝑘2𝑘)+𝑘22−𝑘22𝑘𝑘2sin(𝑘𝑘)sinh(𝑘2𝑘),cos⁡(kℓ)=cos⁡(
qw)cosh(κ2b)+κ22−q22qκ2sin(qw)sinh(κ2b),
(1)
where ℓ=𝑘+𝑘ℓ=w+b is the unit cell length,
and 𝑘=2𝑘𝑘/ℏ2‾‾‾‾‾‾‾‾√q=2mE/ℏ2 and 𝑘2=2𝑘(𝑘0−𝑘)/ℏ2‾‾‾‾‾‾‾‾‾‾‾‾‾‾√κ2=2m(V0
−E)/ℏ2. For each wave vector k, with values −𝑘<𝑘ℓ≤𝑘π<kℓ≤π, one needs to solve
this equation for E(k). A similar equation holds for E  >  V 0 (replace κ 2  →  ik 2,
where 𝑘2≡2𝑘(𝑘−𝑘0)/ℏ2‾‾‾‾‾‾‾‾‾‾‾‾‾‾√k2≡2m(E−V0)/ℏ2). As is well known, the
periodicity in the problem gives rise to a series of energy bands as a function of wave
vector k, with each band separated by an energy gap. In the case where the wells
illustrated in Fig. 1 are deep, any single well, taken in isolation, would consist of a
number of different energy levels corresponding to states that are bound within each
well. As already stated, when N of these wells are coupled through barriers, each of
these energy levels broadens into N states, forming bands. Numerical solutions to this
and other periodic models with different potential shapes are given in refs6 and7.

Tight-Binding

The tight-binding limit tends to focus on one of these bands, and is used to describe the
dispersion, E(k) for this band. General considerations5 in the tight-binding limit in one
dimension lead to a dispersion of the form

𝑘(𝑘)=𝑘𝑘−2𝑘1cos(𝑘ℓ)−2𝑘2cos(2𝑘ℓ)−2𝑘3cos(3𝑘ℓ)−…E(k)=Eb−2t1cos⁡(kℓ)−
2t2cos(2kℓ)−2t3cos(3kℓ)−…
(2)
The usual interpretation of such a dispersion is that each additional term corresponds to
tunneling of an electron from a well to a further neighbouring well. In other words,
while t 1 represents a tunneling amplitude for an electron to tunnel through one of the
barriers in Fig. 1, t 2 represents a tunneling amplitude for the electron to tunnel through
two of the barriers, and end up (directly) two unit cells away from its initial location.
Given that the electron wavefunctions are exponentially decaying in the barrier regions,
it should be clear that |𝑘1|≫|𝑘2|≫|𝑘3|≫…|t1|≫|t2|≫|t3|≫… in this limit. In
what follows we will first focus on nearest-neighbour tunneling amplitudes only, i.e. we
will obtain from Eq. (1), an explicit expression for t 1.
Motivated by the case when V 0 or b is suitably large, one can rewrite Eq. (1) to obtain,
without approximation,

(cos𝑘𝑘2−𝑘𝑘2sin𝑘𝑘2)(cos𝑘𝑘2+𝑘2𝑘sin𝑘𝑘2)=𝑘1(𝑘)+𝑘2(cosqw2−qκ2sinqw
2)(cosqw2+κ2qsinqw2)=η1(k)+η2
(3)
where

𝑘1(𝑘)𝑘2==2𝑘−𝑘2𝑘cos(𝑘ℓ)−𝑘−2𝑘2𝑘(cos𝑘𝑘2−𝑘2𝑘sin𝑘𝑘2)(cos𝑘𝑘2+𝑘𝑘2sin𝑘𝑘2).η1(k
)=2e−κ2bcos(kℓ)η2=−e−2κ2b(cosqw2−κ2qsinqw2)(cosqw2+qκ2sinqw2).
(4)
Written in this way, it is easy to see that when there is no coupling between the wells
(e.g. put b  →  ∞) and therefore both η 1(k)  →  0 and η 2  →  0, then the vanishing of
the first (second) factor on the LHS of Eq. (3) corresponds to determining the energy for
the even (odd) bound states in the single well. It is convenient to define dimensionless
variables as before, specifically z  ≡  qw/2 and z 0  ≡  k 0 w/2,
where 𝑘0≡2𝑘𝑘0/ℏ2‾‾‾‾‾‾‾‾√k0≡2mV0/ℏ2. Then Eq. (3) reads
(cos𝑘−𝑘𝑘20−𝑘2‾‾‾‾‾‾‾√sin𝑘)(cos𝑘+𝑘20−𝑘2‾‾‾‾‾‾‾√𝑘sin𝑘)=𝑘1(𝑘)+𝑘2,(cosz−
zz02−z2sinz)(cosz+z02−z2zsinz)=η1(k)+η2,
(5)
where we have used 𝑘2𝑘/2=𝑘20−𝑘2‾‾‾‾‾‾‾√κ2w/2=z02−z2 and now
𝑘1(𝑘)=2𝑘−2𝑘𝑘𝑘20−𝑘̃ 21√cos𝑘ℓη1(k)=2e−2bwz02−z~12coskℓ
(6)
and

𝑘2=𝑘−4𝑘𝑘𝑘20−𝑘̃ 21√(cos𝑘−𝑘20−𝑘2‾‾‾‾‾‾‾√𝑘sin𝑘)(cos𝑘+𝑘𝑘20−𝑘2‾‾‾‾‾‾‾√sin𝑘).
η2=e−4bwz02−z~12(cosz−z02−z2zsinz)(cosz+zz02−z2sinz).
(7)
Eq. (5) is still exact; now we can imagine the scenario where 𝑘/ℓb/ℓ is very large, and
hence the RHS of this equation is very small. The zeroth order solution for the even
bound states is given by setting the first factor on the LHS of Eq. (5) to zero,
cos𝑘̃ 1−𝑘̃ 1𝑘20−𝑘̃ 21‾‾‾‾‾‾‾√sin𝑘̃ 1=0,cosz~1−z~1z02−z~12sinz~1=0,
(8)
and this determines the zeroth order solution, 𝑘̃ 1z~1. The equation to
determine 𝑘̃ 1z~1 can be written as
tan𝑘̃ 1=(𝑘0𝑘̃ 1)2−1‾‾‾‾‾‾‾‾‾√,tanz~1=(z0z~1)2−1,
(9)
which is the equation that determines the even bound state energies for a particle in
a single well of width w and depth V 0. The solution is shown graphically in Fig. 2. An
actual number for 𝑘̃ 1z~1, slightly less than π/2, is readily obtained for the lowest
bound state, either numerically or on a calculator.
Figure 2
Graphical solution of Eq. (9), for an example z 0 = 2.8π. The LHS is shown with the thin solid
(green) curves, with the obvious characteristic branches of the tan function. The thicker
solid (red) curve represents the RHS. The intersections of these two curves represent
the even bound states and are indicated by open squares; the lowest energy solution is just
below 𝑘̃ 1=𝑘/2z~1=π/2. For completeness we have also drawn the LHS and RHS for the odd
bound states. The LHS is given by tan(𝑘̃ 1−𝑘/2)tan⁡(z~1−π/2) and is shown with thin dashed
(blue) curves. The RHS is the same solid (red) curve as for the even states. Their
intersections are indicated by filled squares. For our tight binding solutions we will focus
on the lowest energy (even) bound state, i.e. the point with 𝑘̃ 1<~𝑘/2z~1<~⁡π/2.
Full size image
First-order in tunneling
A more accurate solution to Eq. (5) can be obtained to 1st order in η 1(k) by
writing 𝑘=𝑘̃ 1[1+𝑘̃ (𝑘)]z=z~1[1+ρ~(k)], and expanding that equation to 1st order
in 𝑘̃ (𝑘)ρ~(k). After some algebra (see Appendix C) we obtain
𝑘̃ (𝑘)=−2𝑘20(𝑘20−𝑘̃ 21)(1+𝑘20−𝑘̃ 21‾‾‾‾‾‾‾√)𝑘−2𝑘𝑘𝑘20−𝑘̃ 21√cos𝑘ℓ.ρ~(k)=−2z02(
z02−z~12)(1+z02−z~12)e−2bwz02−z~12coskℓ.
(10)
Note that (for now) we have ignored η 2, as that factor is exponentially suppressed with
respect to η 1(k). Using the energy scale E 0  =  ħ 2/(2mw2) as before, we find for the
energy to 1st order in η 1(k),
𝑘𝑘0=4𝑘̃ 21−(4𝑘̃ 1𝑘0)2𝑘20−𝑘̃ 211+𝑘20−𝑘̃ 21‾‾‾‾‾‾‾√𝑘−2𝑘𝑘𝑘20−𝑘̃ 21√cos𝑘ℓEE0=4z
~12−(4z~1z0)2z02−z~121+z02−z~12e−2bwz02−z~12coskℓ
(11)
which has the functional form of nearest-neighbour tight-binding (see Eq. (2)). A
comparison of this result (dotted blue curve) with the exact result (solid red curve) is
shown in Fig. 3 as a function of wave vector for particular values of V 0 and 𝑘/ℓb/ℓ.
Figure 3

Comparison of various approximations with the exact result (solid (red) curve). All results
are for 𝑘/ℓ=0.2b/ℓ=0.2 and are for (a) v 0 = 50, (b) v 0 = 100, (c) v 0 = 200, and (d) v 0 = 1000.
In (a), for example, the first-order result is given by Eq. (11) (shown as the dashed (blue)
curve) with the exact result determined numerically from Eq. (1) (shown as the solid (red)
curve). Note that there remains a significant discrepancy. The zeroth-order result, a
constant given by the first term only in Eq. (11), is shown as the horizontal (pink) line [e.g.
at E b /E 0 ≈ 5.94 in (a)]. With further second-order corrections that arise from η 2 and the
nonlinear nature of Eq. (5), we also show the results from Eq. (16). This result now agrees
very well with the exact result, and includes terms corresponding to
−2𝑘2cos(2𝑘ℓ)2t2cos(2kℓ) in Eq. (2). Notice that for the last case, all curves and points are
essentially in agreement. Given the reduction in the scale of the bandwidth in (a) → (d), this
is impressive agreement.
Full size image
If we first focus on case (a) in Fig. 3, the first-order result has significant disagreement
with the exact result. It is indeed true that improved agreement is readily attained by
using deeper wells, as is clear from the progression through (b–d). However, as we now
illustrate, more accurate solutions are achievable by including contributions from η 2,
which is already 2nd order in e −x, where 𝑘≡2𝑘𝑘𝑘20−𝑘̃ 21‾‾‾‾‾‾‾√x≡2bwz02−z~12—
see Eq. (7).
Second-order in tunneling
We first repeat the steps leading to Eq. (10), i.e. we write the solution
as 𝑘≈𝑘̃ 1(1+𝑘̃ (𝑘))z≈z~1(1+ρ~(k)), but now expand to 2nd order in 𝑘̃ (𝑘)ρ~(k) as
well as in e −x, since η 2/η 1(k)  ≈  O(e −x). A straightforward calculation gives
−𝑘̃ (𝑘)𝑘0𝑘1{1−𝑘̃ (𝑘)𝑘1}=2𝑘−𝑘cos𝑘ℓ+2𝑘02𝑘𝑘𝑘−𝑘𝑘̃ (𝑘)𝑘̃ 21−𝑘̃ 2‾‾‾‾‾‾√co
s𝑘ℓ+2𝑘−2𝑘(1−2𝑘̃ 2),−ρ~(k)z0f1{1−ρ~(k)g1}=2e−xcoskℓ+2z02bwe−xρ~(k)δ~21−
δ~2coskℓ+2e−2x(1−2δ~2),
(12)
where

𝑘1𝑘1==1−𝑘̃ 21−𝑘̃ 2√+1𝑘01−𝑘̃ 21−𝑘̃ 21−𝑘̃ 2√+32𝑘01−𝑘̃ 2√+1𝑘0,f1=1−δ~21−δ~2+1z0g1=1−δ~

21−δ~21−δ~2+32z01−δ~2+1z0,
(13)
and 𝑘̃ ≡𝑘̃ 1/𝑘0δ~≡z~1/z0. Eq. (12) is a quadratic in 𝑘̃ (𝑘)ρ~(k); since this is a small
quantity we can simply iterate to obtain 𝑘̃ (𝑘)ρ~(k) explicitly:
𝑘̃ (𝑘)=−2𝑘0𝑘1𝑘−𝑘cos𝑘ℓ−2𝑘1𝑘0𝑘−2𝑘(1−2𝑘̃ 2−𝑘1𝑘0(𝑘1+𝑘02𝑘𝑘𝑘̃ 21−𝑘̃ 2√))+2𝑘21𝑘20𝑘
−2𝑘(𝑘1+𝑘02𝑘𝑘𝑘̃ 21−𝑘̃ 2√)cos2𝑘ℓ.ρ~(k)=−2z0f1e−xcoskℓ−2f1z0e−2x(1−2δ~2−f1z0(g
1+z02bwδ~21−δ~2))+2f12z02e−2x(g1+z02bwδ~21−δ~2)cos2kℓ.
(14)
Finally, we use

𝑘(𝑘)=4𝑘0𝑘̃ 21(1+𝑘̃ )2E(k)=4E0z~12(1+ρ~)2

(15)
from which we obtain

𝑘(𝑘)=𝑘𝑘−2𝑘1cos𝑘ℓ−2𝑘2cos2𝑘ℓ,E(k)=Ec−2t1coskℓ−2t2cos2kℓ,
(16)
where the parameters defined by Eq. (16) are given by
 𝑘1=8𝑘0𝑘0𝑘̃ 2𝑘1𝑘−𝑘,t1=8E0z0δ~2f1e−x,
(17)
𝑘2=−8𝑘0𝑘̃ 2𝑘21(𝑘1+12+𝑘02𝑘𝑘𝑘̃ 21−𝑘̃ 2‾‾‾‾‾‾√)𝑘−2𝑘t2=−8E0δ~2f12(g1+12+z
02bwδ~21−δ~2)e−2x
(18)
and

𝑘𝑘=𝑘0{4𝑘̃ 21−16𝑘̃ 1𝑘̃ 𝑘1𝑘−2𝑘(1−2𝑘̃ 2)}−2𝑘2.Ec=E0{4z~12−16z~1δ~f1e−2x(1

−2δ~2)}−2t2.
(19)
Note that the expansion is governed by the exponential suppression contained in
the e −x and e −2x factors. However, we expect z 0  >  1 for tight-binding, whereas
Fig. 2 makes it clear that 𝑘̃ 1z~1 is of order unity or lower; more
precisely, 𝑘̃ 1<min(𝑘0,𝑘/2)z~1<min(z0,π/2), and so 𝑘̃ <1δ~<1 as well. We have
written the above expressions to make these expansion parameters clear; thus, even
within the expression for t 2, for example, various terms will contribute significantly less
than others. Both f 1 and g 1 are of order unity.

Discussion

The more accurate result from Eq. (16) is plotted in Fig. 3 (as indicated by the square
symbols), and gives good agreement for the parameters used in that figure. Note
that t 1 is given by an expression identical to the one implied in Eq. (11)—by going to
2nd order in e −x this has not changed, and in fact is identical to the expression derived for
the double-well in Appendix A, Eq. (A5). The need to to go to 2nd order and therefore
generate a term with cos(2𝑘ℓ)cos(2kℓ) wave vector dependence is sometimes
interpreted to mean that a significant tunneling amplitude exists between second-
nearest-neighbour atoms. The fact that this is required even for the case of the double-
well studied in Appendix A (where there is no second-nearest neighbour!) indicates
that this interpretation is incorrect. Indeed it is a difficult problem to disentangle
contributions to 2nd order from next-nearest-neighbour tunneling and contributions
arising from the inherent non-linear nature of the equations; at this point we simply
caution that all these contributions are not entirely due to direct next-nearest-neighbour
tunneling.
For completeness, in Fig. 4 we fix the well depth to be v 0  ≡  V 0/E 0  =  50 and show
the dispersions for a variety of different barrier widths. The trends are the same in the
two cases, except that the 2nd order result is slightly less accurate for the least tightly
bound case considered [see (a)]. With increasing barrier width, however, as in Fig. 3,
both the 2nd-order and the 1st-order results become increasingly accurate. Note the
change in scale as v 0 and 𝑘/ℓb/ℓ increase in Figs 3 and 4, respectively; in both cases the
results approach the single well result while a well-defined dispersion remains.
Figure 4

As in Fig. 3, a comparison of various approximations with the exact result (solid (red)
curve) for a variety of barrier widths, all with v 0 ≡ V 0/E 0 = 50. We use barrier widths of
(a) 𝑘/ℓ=0.1b/ℓ=0.1, (b) 𝑘/ℓ=0.2b/ℓ=0.2, (c) 𝑘/ℓ=0.3b/ℓ=0.3 and (d) 𝑘/ℓ=0.4b/ℓ=0.4. By
examining the vertical scales, a clear progression towards more tightly bound wells is
evident. Moreover, the first case considered shows not perfect agreement, even when
2nd order corrections are included. As 𝑘/ℓb/ℓ increases, agreement quickly improves,
especially when account is made of the steady reduction in the scale of the bandwidth. For
all cases, the horizontal (pink) line corresponds to the bound state energy for a single well
and corresponds to the constant given by the first term only in Eq. (11). The approximate
result with the 1st order correction only, the full Eq. (11), is shown as a dashed (blue) curve,
while the approximate results including 2nd order corrections from Eq. (16) are given by the
square (green) symbols.
Full size image
In both Figs 3 and 4 it should be clear that for the more strongly coupled wells (e.g. (a)
and (b) in particular) a significant amount of electron-hole asymmetry is present. In
Fig. 5 the effective mass ratio, |m h /m e | is shown for various values of the barrier
thickness as a function of well depth. Here, the electron mass, m e is defined in the usual
way (see the caption in Fig. 5) through the curvature at k  =  0 and similarly for the hole
mass, m h . As discussed in ref.6 an asymmetry is expected on general grounds since
holes are by definition closer to the top of the barriers than electrons. They should
therefore have lower masses for this reason alone, and this is reflected in the results of
Fig. 5, where all the ratios are lower than unity. The thicker curves are from the exact
calculations while the thinner curves (in too good agreement with the exact results to be
visible for most of the parameter space shown) are readily determined from the tight-
binding parametrization of Eq. (16). These are fairly accurate when the higher-order
correction considered above is included.

Figure 5

Absolute value of the effective mass ratio, |m h /m e | vs. v 0 ≡ V 0/E 0 for the various values of
barrier width 𝑘/ℓb/ℓ, as indicated. Here 𝑘−1𝑘≡∂2𝑘(𝑘)/𝑘0∂(𝑘ℓ)2me−1≡∂2E(k)/E0∂(kℓ)2 at k = 0
and 𝑘−1ℎ≡∂2𝑘(𝑘)/𝑘0∂(𝑘ℓ)2mh−1≡∂2E(k)/E0∂(kℓ)2 at 𝑘=𝑘/ℓk=π/ℓ. The thick curves are the exact
result, determined from Eq. (1), while the thinner curves are determined from the tight-
binding parametrization of Eq. (16). These latter curves are barely visible over almost the
entire parameter regime shown, indicating that when the 2nd order corrections considered
are included the derived tight-binding parameters are very accurate.
Full size image
Figure 5 exemplifies what is perhaps the primary result of this calculation—that
electron-hole asymmetry is the “rule”, not the exception. In the past three decades, as
more materials with exotic properties (superconductivity, magnetoresistance, etc.) have
been engineered, particularly through doping, and electron-hole-doping symmetry
has not been observed, strong correlations are often suggested as a possible explanation.
The present work notes that the usual starting point, tight-binding with nearest-
neighbour hopping only, tends to bias the expectation in favour of electron-hole
symmetry, when in fact the opposite is true. Our calculations illustrate that even where
merely nearest-neighbour hopping seems like a good physically-motivated assumption,
the band structure (before invoking interaction terms) will be already electron-hole
asymmetric. For example, Hirsch and one of the present authors11 suggested a
modulated hopping model in which one of the interactions is explicitly particle-hole
asymmetric in a tight-binding framework (see ref.12 for an overview of the physics of
hole superconductivity). It follows that many of the properties of this model will exhibit
electron-hole asymmetries. An accurate confrontation with experiment will required
some knowledge of the asymmetry already possibly present in the band structure, not
necessarily because of a next-nearest-neighbour hopping term, but for the reasons
suggested in this paper—the smaller tunneling barrier faced by holes compared to
electrons.

Summary

We have succeeded in deriving the effective model for the periodic potential first used
to model a solid, the so-called Kronig-Penney model, consisting of a series of wells and
barriers. As is more readily illustrated for the double-well potential, one can achieve
very high accuracy by exploiting the tightly-bound limit, where two neighbouring wells
are well separated. This ensures that the tunneling amplitude between the two wells is
very small, and one can essentially use perturbation theory with respect to this “atomic
limit”.

The generalization of this process to an infinite array of wells and barriers is

straightforward. However, incorporating tunneling to 1storder (meaning terms of
order e −x, where 𝑘∝𝑘𝑘0‾‾‾√x∝bV0) provided only a qualitative agreement with the
exact result (this would become quantitative for sufficiently large 𝑘/ℓb/ℓ and/or V 0).
When including terms of 2nd order in e −x, very good quantitative agreement was
achieved, even for moderate well depths. Terms of order e −2x would necessarily be
accompanied by dispersive terms like cos(2𝑘ℓ)cos(2kℓ), which are generally
associated with next-nearest-neighbour tunneling, i.e. tunneling across two barriers. By
comparison with results of a simple double-well, where terms of order e −2x also
contribute to the energy, we were able to show that terms of this order were not
exclusively associated with such longer-range tunneling. Instead, inherent non-linearity
of the equations governing the electronic energy dispersion will naturally give rise to
such terms, even in the absence of next-nearest-neighbour tunneling.
It is useful to map the complete microscopic double-well problem onto the two-state
system that is often used to describe this problem in simplified terms. Similarly, it is
useful to map the microscopic problem of an infinite array of wells onto a simplified
model—this is the tight-binding description. We have carried out such a mapping, with
no “fitting” involved and we have illustrated the accuracy as well as the limitations of
such a mapping.