Physics Course For Students

ELEMENTS
OF
MODERN PHYSICS
Dr. Ing. Valeric
a D. Ninulescu
Contents
1 The experimental foundations of quantum mechanics
1.1 Thermal radiation . . . . . . . . . . . . . . . . . . . . . . . .
1.1.1 Quantitative laws for blackbody radiation . . . . . . .
1.2 Photoelectric effect . . . . . . . . . . . . . . . . . . . . . . . .
1.3 Waveparticle duality of radiation . . . . . . . . . . . . . . .
1.4 Compton effect . . . . . . . . . . . . . . . . . . . . . . . . . .
1.5 Atomic spectra . . . . . . . . . . . . . . . . . . . . . . . . . .
1.6 Bohr model of the hydrogen atom . . . . . . . . . . . . . . .
1.7 Correspondence principle . . . . . . . . . . . . . . . . . . . .
1.8 Einsteins phenomenological theory of radiation processes . .
1.8.1 Relations between Einstein coefficients . . . . . . . . .
1.8.2 Spontaneous emission and stimulated emission as competing processes . . . . . . . . . . . . . . . . . . . . .
1.9 Experimental confirmation of stationary states . . . . . . . .
1.10 Waveparticle duality of matter . . . . . . . . . . . . . . . . .
1.10.1 DavissonGermer experiment . . . . . . . . . . . . . .
1.11 Heisenberg uncertainty principle . . . . . . . . . . . . . . . .
1.11.1 Uncertainty relation and the Bohr orbits . . . . . . . .
1.12 Questions and problems . . . . . . . . . . . . . . . . . . . . .
23
24
26
27
30
32
32
2 Postulates of quantum mechanics and applications

2.1 First postulate . . . . . . . . . . . . . . . . . . . . .
2.2 Schr
odinger equation . . . . . . . . . . . . . . . . . .
2.3 Probability conservation . . . . . . . . . . . . . . . .
2.4 Constraints on the wavefunction . . . . . . . . . . .
2.5 Time-independent Schr
odinger equation . . . . . . .
2.6 Potential wells . . . . . . . . . . . . . . . . . . . . .
2.7 The one-dimensional infinite well . . . . . . . . . . .
2.7.1 Introduction . . . . . . . . . . . . . . . . . .
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1
2
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CONTENTS
iv
2.7.2 Energy eigenvalues and eigenfunctions . . . . . . . . .

2.7.3 Discussion . . . . . . . . . . . . . . . . . . . . . . . . .
2.8 The rectangular potential barrier. Potential barrier penetration
2.8.1 Case 0 < E < V0 . . . . . . . . . . . . . . . . . . . . .
2.8.2 Case E > V0 . . . . . . . . . . . . . . . . . . . . . . .
2.8.3 Discussion . . . . . . . . . . . . . . . . . . . . . . . . .
2.9 The quantum harmonic oscillator . . . . . . . . . . . . . . . .
2.10 Three-dimensional Schr
odinger equation . . . . . . . . . . . .
2.10.1 Example: The three-dimensional infinite well . . . . .
2.11 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
A Fundamental physical constants
51
55
56
56
59
59
60
66
67
69
73
B Greek letters used in mathematics, science, and engineering 77
Preface
This text has grown out of an introductory course in modern physics
taught to second year undergraduates at the Faculty of Engineering in Foreign Languages, Politehnica University of Bucharest. It was intended from
the beginning that the book would include all the essentials of an introductory course in quantum physics and it would be illustrated whenever
appropriate with thechnical applications.
A set of solved problems is included at the end of each chapter.
V. Ninulescu
2011
vi
CONTENTS
Glossary of notations
e
i
Im(.)
R
c.c.
z
v
h.i
R
r
A
A
kB
CM
lhs
rhs
1-D
TDSE
TISE
exponential function, ez = exp(z)

complex unity, i2 = 1
imaginary part of a complex number
the set of real numbers
complex conjugate of the expression written in front of c.c.
complex conjugated of z
vector
average
integral over the whole three-dimensional space
operator A
adjoint of A
roughly similar; poorly approximates
Boltzmann constant
centre of mass
left hand side
right hand side
one-dimensional
time-dependent Schr
odinger equation
time-independent Schr
odinger equation
Chapter 1
The experimental
foundations of quantum
mechanics
At the end of the 19th century, it seemed that physics was able to explain all physical processes. According to the ideas of that time, the Universe
was composed of matter and radiation; the matter motion could be studied
by Newtons laws and the radiation was described by Maxwells equations.
Physics of that time is now called classical physics. The theory of special relativity (Albert Einstein, 1905) generalized classical physics to include
phenomena at high velocities.
This confidence began to disintegrate due to the inability of the classical
theories of mechanics and electromagnetism to provide a satisfactory explanation of some phenomena related to the electromagnetic radiation and the
atomic structure. This chapter presents some physical phenomena that led
to new ideas such us the quantization of the physical quantities, the particle
properties of radiation, and the wave properties of matter. Certain physical
quantities, such as energy and angular momentum, were found to take on
a discrete, or quantized, set of values in some conditions, contrary to the
predictions of classical physics. This discreteness property gave rise to the
name of quantum mechanics for the new theory in physics.
Quantum mechanics reveals the existence of a universal physical constant, Plancks constant, whose present day accepted value in SI units is
h = 6.626 068 96(33) 1034 J s .
Its small value when measured in the macroscopic units of the SI shows that
quantum physics is basically used at much smaller levels, such as the atomic
and subatomic levels.
1.1
Thermal radiation
It is well known that every body with non-zero absolute temperature

emits electromagnetic radiation with a continuous spectrum that contains
all wavelengths. Let us explain this phenomenon in the frame of classical
physics. Atoms and molecules are composed of charged particles. The irregular thermal motion produces irregular oscillatory motion of the electrons
inside atoms, characterized by a continuous spectrum of frequencies. Since
an oscillation is accelerated motion, each oscillation at a particular frequency
leads to the emission of electromagnetic radiation of the same frequency.
Examples of thermal radiation include the solar radiation, the visible
radiation emitted by a light bulb, or the infrared radiation of a household
radiator.
The radiation incident on the surface of a body is partially reflected and
the other part is absorbed. Dark bodies absorb most of the incident radiation
and light bodies reflect most of the radiation. For example, a surface covered
with lampblack absorbs about 97 % of the incident light and polished metal
surfaces, on the other hand, absorb only about 6 % of the incident radiation,
reflecting the rest. The absorptance (absorption factor ) of a surface is
defined as the ratio of the radiant energy absorbed to that incident upon it;
this quantity is dependent on wavelength, temperature, and the nature of
the surface.
Suppose a body at thermal equilibrium with its surroundings. Such a
body emits and absorbs the same energy in unit time, otherwise its temperature can not remain constant. The radiation emitted by a body at thermal
equilibrium is termed thermal radiation.
A blackbody is an object that absorbs all electromagnetic radiation falling
on it.1 This property refers to radiation of all wawelengths and all angles
of incidence. However, a blackbody is an abstraction that does not exist in
the real world. The best practical blackbody is the surface of a small hole
in a container maintained at a constant temperature and having blackened
interior, because any radiation entering through the hole suffers multiple
reflections, a lot getting absorbed on each reflection, and ultimately is completely absorbed inside (Fig. 1.1). Consider now the reverse process in which
1
The term arises because such bodies do not reflect incident visible radiation, and
therefore appear black.
1.1 Thermal radiation

y
T = const

}
7
Fig. 1.1 A cavity with a small hole behaves as

a perfect absorber. The inner walls are blackened and maintained at temperature T = const.
R

radiation emitted by the interior cavity walls escapes through the hole. The
interior walls are constantly radiating and reabsorbing their own radiation
and after a while the state of thermal equilibrium is attained.2 A small fraction of this radiation is incident upon the hole and pass through it. Since
the surface behaves as a blackbody, the radiation that escapes the cavity has
the properties of a blackbody radiator. The study of the cavity radiation
led Gustav Robert Kirchhoff to the conclusion that blackbody radiation is
homogeneous, isotropic, nonpolarized, independent of the nature of the walls
or the form of the cavity.
The ability of a surface to emit thermal radiation is characterized by its
emittance , defined as the ratio of the radiant energy emitted by a surface to
that emitted by a blackbody at the same temperature. As the absorptance,
the emittance depends on wavelength, temperature, and the nature of the
surface.
The emittance of a surface can be related to its absorptance as follows.
Suppose the surface of the interior cavity in Fig. 1.1. Let us denote by L
the spectral radiance inside the cavity (power per unit surface per unit solid
angle per unit frequency interval). Taking into account that at equilibrium
the walls emit as much as they absorb, we have L = L , so that
= .
(1.1)
This result is known as Kirchhoff s radiation law (1859). According to

Eq. (1.1), objects that are good emitters are also good absorbers. For example, a blackened surface is an intense emitter surface as well as an intense
absorber one.
2
The small size of the hole ensures that neither the radiation which enters the cavity
from outside, nor that which escapes outside, can alter the thermal equilibrium in the
cavity.
A grey body is defined as a body with constant emittance/absorptance

over all wavelengths and temperatures. Such an ideal body does not exist
in practice but this assumption is a good approximation for many objects.
The laws governing the emission or absorption of thermal radiation by
blackbodies have a universal character and is therefore of special interest.
1.1.1
Quantitative laws for blackbody radiation
StefanBoltzmann law
The radiant exitance (energy radiated from a body per unit area per unit
time), M , of a blackbody at temperature T grows as T 4 :
M (T ) = T 4 ,
(1.2)
where 5.67 108 W m2 K4 is StefanBoltzmann constant. The law

was first formulated in 1879 by Josef Stefan as a result of his experimental
measurements; the same law was derived in 1884 by Ludwig Boltzmann from
thermodynamic considerations.
StephanBoltzmann law can be extended to a grey body of emittance
as
(1.3)
M (T ) = T 4 .
Wiens displacement law
Wilhelm Wien experimental studies on the spectral distribution of blackbody radiation revealed:
the radiative power per wavelength interval has a maximum at a certain
wavelength max ;
the maximum shifts to shorter wavelengths as the temperature T is
increased.
Wiens displacement law (1893) states that the wavelength for maximum
emissive power from a blackbody is inversely proportional to its absolute
temperature,
max T = b .
(1.4)
The constant b is called Wiens displacement constant and its value is b
2.898 103 m K .
For example, when iron is heated up in a fire, the first visible radiation is
red. Further increase in temperature causes the colour to change to orange,
1.1 Thermal radiation
then yellow, and white at very high temperatures, signifying that all the
visible frequencies are being emitted equally.
Wiens displacement law can be used to determine the temperature of a
blackbody spectroscopically by measuring the wavelength at which the intensity of the radiation is maximum. This method has been used extensively
in determining stellar temperatures.
RayleighJeans law. Ultraviolet catastrofe
The spectral distribution of blackbody radiation is specified by the spectral radiant exitance M that is, emitted power per unit of area and unit of
wavelength. In an attempt to furnish a formula for M , it proves convenient
to focus our attention on the radiation inside a cavity. Let denote the
spectral radiant energy density, which is defined as the energy per unit of
volume and unit of wavelength. It can be shown that (see Problem 1.6)
M = (1/4)c ,
(1.5)
where c is the speed of light in vacuum.

It is also useful to consider the spectral quantities as functions of frequency instead of wavelength. Based on the relationship = c/ , the
radiation with the wavelength inside the interval (, + d) has the frequency between d and , where d = |d/d| d = (c/)2 d . Now, the
spectral radiant exitance in terms of frequency M and the spectral radiant
exitance in terms of wavelength M are related by
M () d = M () d .
(1.6)
() d = () d .
(1.7)
Similarly,
The classical physics result for is
(, T ) =
8 2
kB T ,
c3
(1.8)
known as RayleighJeans formula. The comparison with the experimental

results shows a good agreement for small frequencies. However, do not
exhibite a maximum, being an increasing function of frequency. More than
that, the radiant energy density is
Z
Z
8kB T 2
(T ) =
(, T ) d =
d = ,
c3
0
0
an unacceptable result, known as the ultraviolet catastrophe.
Plancks radiation law

In 1900 Max Planck determined a formula which agrees with the experiment at whatever frequency based on a new and revolutionary idea: the
exchange of energy between a body and its surroundings can be performed
only in discrete portions, the minimum energy implied in the exchange being
proportional to the frequency, h. Planck radiation law reads
(, T ) =
8 2
h
.
c3 exp(h/kB T ) 1
(1.9)
The constant h is called Plancks constant and has the value h 6.626
1034 J s .
By use of Eq. (1.7), we get
(, T ) =
8hc
1
.
5 exp(hc/kB T ) 1
(1.10)
To express the radiant exitance E , Eq. (1.5) is used:

E (, T ) =
2hc2
1
.
5 exp(hc/kB T ) 1
(1.11)
Plancks radiation formula contains all the information previously obtained. Figure 1.2 presents the graph of the spectral energy density (, T )
given by Eq. (1.10).
Applications
Pyrometer: device for measuring relatively high temperatures by measuring radiation from the body whose temperature is to be measured.
Infrared thermography: a fast non-distructive inspection method that
maps the temperature differences of any object in a range from 50 C
to 1500 C.
1.2
Photoelectric effect
The photoelectric effect consists in the ejection of electrons from a solid

by an incident electromagnetic radiation of sufficiently high frequency. This
frequency is in the visible range for alkali metals, near ultraviolet for other
metals, and far ultraviolet for non-metals. The ejected electrons are called
photoelectrons.
1.2 Photoelectric effect
2000 K
(,T), 103J m4
5
4
1750 K
3
2
1500 K
1
1000 K
0
0
, m
Fig. 1.2 Spectral energy density (, T ) of a blackbody at a few temperatures.

UV radiation
quartz window
A
Fig. 1.3 Experimental arrangement for
the study of the photoelectric effect.
Vacuum chamber
A
U
The phenomenon was first observed by Heinrich Hertz in 1887; he noticed

that the minimum voltage required to draw sparks from a pair of metallic
electrodes was reduced when they were illuminated by ultraviolet radiation.
Wilhelm Hallwachs (1888) found that when ultraviolet radiation was incident
on a negatively charged zinc surface, the charge leaked away quickly; if
the surface was positively charged, there was no loss of charge due to the
incident radiation. More than that, a neutral surface became positively
charged when illuminated by ultraviolet radiation. It is evident that only
negative charges are emitted by the surface under its exposing to ultraviolet
radiation. Joseph John Thomson (1899) established that the ultraviolet
radiation caused electrons to be emitted, the same particles found in cathode
rays.
8
i
6
3I
2I
I
U0
Fig. 1.4 Photocurrent (i) versus potential difference (U ) between cathode and anode for different values of the intensity (I,
2I, and 3I) of the monochromatic beam of
light.
-U
A typical arrangement for the study of the photoelectric effect is depicted

in Fig. 1.3. A vacuumed glass tube contains two electrodes (A = anode =
collecting plate, C = cathode) and a quartz window allowing light to shine
on the cathode surface. The electrons are emitted at the cathode, fall on
the anode, and complete a circuit. The resulting current is measured by
a sensitive ammeter. It is very important that the surface of the cathode
is as clean as possible. An adjustable potential difference U of a few volts
is applied across the gap between the cathode and the anode to allow the
photocurrent control.
If A is made positive with respect to C, the electrons are accelerated
toward A. When all electrons are collected, the current saturates.
If A is made negative with respect to C, the electric field tends to repel
the electrons back towards the cathode. For an electron to reach the
collecting plate, it must have a kinetic energy of at least eU , where e
is the magnitude of the electron charge and U is the retarding voltage.
As the repelling voltage is increased, fewer electrons have sufficient
energy to reach the plate, and the current measured by the ammeter
decreases. Let U0 denote the voltage where the current just vanishes;
the maximum kinetic energy of the emitted electrons is
2
(1/2)mvmax
= eU0 ,
(1.12)
where m denotes the mass of the electron. U0 is called stopping potential (voltage).
The experimental results for a given emitting cathode are sketched in
Figs. 1.4 and 1.5. From Fig. 1.4 it is clear that for a given metal and
frequency of incident radiation, the rate at which photoelectrons are ejected
is proportional to the intensity of the radiation. Figure 1.5 reveals other
two results. First, a given surface only emits electrons when the frequency
of the radiation with which it is illuminated exceeds a certain value; this
1.2 Photoelectric effect
2
(1/2)mvmax
6
Fig. 1.5 Dependence of the maximum kinetic
energy of photoelectrons on the frequency of the
incident radiation.
0
frequency, 0 in Fig. 1.5, is called threshold frequency. It is experimentally

proven that 0 depends on the cathode material. Secondly, the energy of the
photoelectrons is independent of the radiation intensity, but varies linearly
with the radiation frequency. The experiment also shows that there is no
significant delay between irradiation and electron emission (less than 109 s).
The minimum energy needed to extract the electron from the material
is called work function. If the electron absorb a larger energy then , the
energy in excess is kinetic energy of the photoelectron.
The experimental results disagree with the Maxwell wave theory of light:
According to this theory, as the electromagnetic wave reaches the surface, the electron start to absorb energy from the wave. The more
intense the incident wave, the greater the kinetic energy with which
the electrons should be ejected from the surface. In contrast, the experiment shows that the increase of the wave intensity produces an
increase in the number of photoelectrons, but not their energy.
The wave picture predicts the occurence of the photoelectric effect for
any radiation, regardless of frequency.
There should be a significant delay between the surface irradiation and
the release of photoelectrons (see Problem 1.8).
In order to account for the photoelectric effect experimental results,
Albert Einstein (1905) proposed a new theory of light. According to this
theory, light of fixed frequency consists of a collection of indivisible discrete packages, called quanta, whose energy is
E = h .
(1.13)
The word photon for these quantized packets of light energy came later,
given by Gilbert Newton Lewis (1926).
Einstein assumed that when light strikes a metal, a single photon interacts with an electron and the photon energy is transferred to the electron. If
10
h > , then the electron is emitted from the surface with residual kinetic
energy
2
= h .
(1.14)
(1/2)mvmax
Otherwise, the electron remains trapped in the metal, regardless of the intensity of the radiation; the threshold frequency of the photoelectric effect
is
0 = /h .
(1.15)
Einstein equation of the photoelectric effect [Eq. (1.14)] exactly explains the
observed dependence of the maximum kinetic energy on the frequency of the
radiation (Fig. 1.5).
Let us continue the explanation of the experimental photoelectric effect
findings. Increasing the intensity of the radiation n times means an n times
increase of the number of photons, while the energy of each individual photon
remains the same. For sufficiently low radiation intensities, it can be assumed
that the probability of an electron to absorb two or more photons is negligibly
small compared to the probability of absorbing a single photon. It follows
that the number of electrons emitted increases also by the factor n . Finally,
no time is necessary for the atom to be heated to a critical temperature and
therefore the release of the electrons is nearly instantaneous upon absorption
of the light.
Combining Eqs. (1.12) and (1.14) we get
U0 = (h/e) /e .
(1.16)
The stopping voltage as a function of the radiation frequency is a straight line

whose slope is h/e and whose intercept with the frequency axis is 0 = /h.
This experimental dependence can be used to calculate Plancks constant
and the work function of the metal. (The value of e is considered as known.)
The result for the Plancks constant is the same as that found for blackbody
radiation; this agreement can be considered as a further justification of the
portion of energy h introduced by Planck. From the observed value of 0 ,
the workfunction is calculated as = h0 . Table 1.1 furnishes the work
function of some chemical elements.
The photoelectric effect is perhaps the most direct and convincing evidence of the corpuscular nature of light. That is, it provides undeniable
evidence of the quantization of the electromagnetic field and the limitations
of the classical field equations of Maxwell. Another evidence in support of
the existence of photons is provided by the Compton effect.
Applications: photocells, photomultiplier
1.3 Waveparticle duality of radiation
11
Table 1.1 Electron work function of some elements [10]. In general, differs for
each face of a monocrystalline sample. Inside the table, polycr is an abbreviation
for polycrystalline sample.
Element
Ag (silver)
Al (aluminum)
Au (gold)
Ca (calcium)
Cr (chromium)
Cs (cesium)
1.3
Plane
100
110
111
100
110
111
100
110
111
polycr
polycr
polycr
/eV
4.64
4.52
4.74
4.20
4.06
4.26
5.47
5.37
5.31
2.87
4.5
1.95
Element
Cu (copper)
Fe (iron)
K (potassium)
Li (lithium)
Mg (magnesium)
Na (sodium)
Rb (rubidium)
Ti (titanium)
Zn (zinc)
Plane
100
110
111
100
111
polycr
polycr
polycr
polycr
polycr
polycr
polycr
/eV
5.10
4.48
4.94
4.67
4.81
2.29
2.93
3.66
2.36
2.261
4.33
3.63
Waveparticle duality of radiation
The phenomena of the interference and diffraction can be explained only

on the hypothesis that radiant energy is propagated as a wave. The results
of the experiments on the photoelectric effect leave no doubt that in its
interaction with matter, radiant energy behaves as though it were composed
of particles; it will be shown later that similar behaviour is observed in the
Compton effect and the processes of emission and absorption of radiation.
The two pictures should be understood as complementary views of the same
physical entity. This is called the waveparticle duality of radiation.
A particle is characterized by its energy and momentum; a wave is characterized by its wave vector and angular frequency. We perform here the
link between the two pictures.
The energy of a photon is given by Eq. (1.13). We complete the characterization of the photon with a formula for its momentum.
Classical electromagnetic theory shows that a wave carries momentum in
addition to energy; the relation between the energy E contained in a region
and the corresponding momentum p is
E = cp .
(1.17)
It is natural to extend this formula for the quantum of radiation, i.e.,

the photon. For a plane wave of wave vector k, the angular frequency of the
12
wave is = k/c and the photon momentum can be written

p=
E
~
=
= ~k .
c
c
(1.18)
This formula can be written with vectors,

p = ~k .
(1.19)
To sum up, the two behaviours of radiation are linked by PlanckEinstein

relations
E = h = ~ and p = ~k .
(1.20)
1.4
Compton effect
The existence of photons is also demonstrated by experiments in which

x-rays or -rays are scattered by a target. The experiments performed in
1922 by Arthur Holly Compton with x-rays and a graphite target show that,
in addition to the incident radiation, there is another radiation present,
of higher wavelenth. The radiation scattering with change in wawelength
is called Compton effect. Given that is the wavelength of the incident
radiation and that of the scattered radiation, Compton found that
does not depend upon the wavelength of the incident rays or upon the target
material; it depends only on the direction of scattering (angle between the
incident wave and direction in which scattered waves are detected) according
to the experimental relation
= C (1 cos ) .
(1.21)
The constant C 2.426 1012 m is nowadays called Compton wavelength

of the electron.
The scattered radiation is interpreted as radiation scattered by free or
loosely bound electrons in the atoms of matter.
The classical treatment of the x-rays or -rays as waves implies that
an electron is forced to oscillate at a frequency equal to that of the wave.
The oscillating electron now acts as a source of new electromagnetic waves
having the same frequency. Therefore, the wavelengths of the incident and
scattered x-rays should be identical. We must therefore conclude that the
classical theory fails in explaining the Compton effect.
Treating the radiation as a beam of photons, a photon can transfer part
of its energy and linear momentum to a loosely bound electron in a collision
1.4 Compton effect
::::Incident
photon
Target
electron
at rest
13
Scattered
* photon
::
::
Fig. 1.6 In Compton scattering an x-ray

photon of wavelength collides with an electron initially at rest. The photon scattered
in the direction has the wavelength > .
Recoil
electron
(Fig. 1.6). Since the energy of a photon is proportional to its frequency, after
the collision the photon has a lower frequency and thus a longer wavelength.
To be more specific, let p = h/c = h/ and p = h /c = h/ be the
momenta of the photon before and after the collision. The electron can be
considered initially at rest. After the collision it acquires a kinetic energy
T = h h = hc/ hc/
(1.22)
and a momentum
h2
h2
h h
+
2
cos ,
(1.23)
2
2
as required by the conservation of energy of momentum. Here, T and pe are

related by the relativistic equation
p
T = c p2e + m2 c2 mc2 .
(1.24)
pe = p p ,
p2e = (p p )2 =
Inserting Eqs. (1.22) and (1.23) into Eq. (1.24), rearranging and squaring,
we get

2
h2 c2 h2 c2
hc hc
hc hc
cos + m2 c4 .
+ mc2 = 2 + 2 2
After performing the elementary calculations it is obtained Eq. (1.21), where

C = h/mc .
(1.25)
The presence of the radiation with the same wavelength as the incident
radiation is not predicted by Eq. (1.21). This radiation is explained by
the scattering of the incident radiation by tightly bound electrons. In this
case, the photon collides with the entire atom, whose mass is considerably
greater than the mass of a single electron. The photon and atom exchange
momentum, but the amount of exchanged energy is much less than in case
of the photonelectron collision; the wavelength shift is not significant.
Compton scattering is of prime importance to radiobiology, as it happens
to be the most probable interaction of high energy x-rays with atomic nuclei
in living beings and is applied in radiation therapy.
14
1.5
Atomic spectra
By the early 1900s, the following observations concerning the atomic

emission spectra had been done:
When a gas of an element at low pressure is subjected to an input of energy, such as from an electric discharge, the gas emits electromagnetic
radiation.
On passing through a very thin slit and then through a prism the electromagnetic radiation can be separated into its component frequencies.
It was found that a gas at low pressure emits only discrete lines on the
frequency scale.
The emission spectrum is made up of spectral series in the different
regions (infrared, visible, and ultraviolet) of the spectrum of electromagnetic radiation; the spectral lines in a series get closer together
with increasing frequency.
Each element has its own unique emission spectrum.
The simpliest line spectrum is that of the hydrogen atom. Its four spectral lines in the visible have wavelengths that can be represented accurately
by the Johann Balmer formula (1885)
n = C
n2
n2 4
n = 3, 4, . . . ,
(1.26)
where C 364.6 nm . This formula was written by Johannes Rydberg (1888)

for wavenumbers,

1
1
1
n =
= R 2 2 , n = 3, 4, . . . ,
n
2
n
where the new constant R is nowadays called Rydberg constant, and generalized in the form

1
1
1
R
R
n1 n2 =
= R 2 2 = 2 2 , n1 = 2, 3, . . . , n2 = 3, 4, . . . ,
n1 n2
n1 n2
n1 n2
(1.27)
and n1 < n2 . Here, n1 defines the spectral series. For a given series, with
increasing values of n2 , the wavenumber approaches the limit R/n21 . The
separation of consecutive wavenumbers of a given series decreases so that
1.6 Bohr model of the hydrogen atom
15
the wavenumber can not exceed the series limit. In principle, an infinite
number of lines lie at the series limit.
According to Eq. (1.27) the wavenumber of any line of the hydrogen
spectrum is the difference of two spectral terms:
n1 n2 = Tn1 Tn2 ,
(1.28)
Tn = R/n2 .
(1.29)
with
It proves empirically that the lines of other chemical elements can also be
expressed as the difference of two terms; however, a spectral term has a more
complicated form.
None of the above quantitative result could be explained satisfactorily in
the frame of clasical physics.
1.6
Bohr model of the hydrogen atom
Atoms have radii on the order of 1010 m . To study the internal structure of atoms, Ernest Rutherford, Hans Geiger and Ernest Marsden (1909)
directed -particles from radioactive radium at thin gold foil. Based on the
results of the -particles scattering by the gold atoms, Rutherford (1911)
furnished the nuclear atom model (planetary model of the atom): the atom
consists of a positively charged heavy core (nucleus) of radius on the order
of 1015 m and a cloud of negatively charged electrons. Atomic structure
was pictured as analogous to the solar system, with the nucleus playing the
role of the Sun and the electrons that of the planets bound in their orbits
by Coulomb attraction to the nucleus.
About as soon as the model was published it was realized that the atom
model suffers from two serious deficiencies:
1. Orbital motion is an accellerated motion and electrons are charged
particles. According to the electromagnetic theory, the electrons should
radiate energy in the form of electromagnetic waves. Electrons lose energy
and they should spiral into the nucleus in a time of the order of 108 s . This
conclusion completely disagrees with experiment, since the atoms are stable.
2. The frequency of the radiated energy is the same as the orbiting one.
As the orbiting frequency can take a continuous range of values, the discrete
emission spectrum of atoms can not be explained.
To overcome these deficiencies, Niels Bohr (1913) improved the Rutherford model of the atom by introducing the following postulates:
16
For every atom there is an infinite number of stationary states in which

the atom can exist without emitting radiation. The energies of the
stationary states,
E1 , E2 , E3 , . . . ,
form a discrete set of values.
Emission and absorption of radiation are always associated to a transition of the atom from one stationary state to another. The frequency
of the radiation emitted or absorbed respectively during such a transition is given by the equation
h = |E2 E1 | ,
(1.30)
where E1 and E2 denote the energy of the atom in the two stationary
states.
Bohr applied these postulates for the hydrogen atom. The electron of
mass m and electric charge e is assumed to move around the nucleus of
electric charge e in a circular orbit. The selection of the allowed stationary
states is performed by the following quantization rule for the angular momentum: the angular momentum of the electron in a stationary state is an
integer multiple of ~:
mvr = n~ ,
where n = 1, 2, 3, . . . .
(1.31)
We are now in a position to solve the problem. Newtons second law

applied for the electron motion on a circular orbit of radius r with the
velocity v under the attractive Coulomb force exerted by the nucleus yields
m
v2
e2
=
.
r
40 r 2
(1.32)
Combining Eqs. (1.31) and (1.32), we find

40 ~2 2
n = a0 n2
me2
(1.33)
e2 1
.
40 ~ n
(1.34)
40 ~2
5.29 1011 m
me2
(1.35)
rn =
and
vn =
The radius
a0 =
1.6 Bohr model of the hydrogen atom
17
is called the Bohr radius. This value sets the scale for atomic dimension.
The potential energy of the electron in the hydrogen atom is given by
V (r) =
e2
.
40 r
(1.36)
The energy of the atom in state n is

1
e2
En = Tn + Vn = mvn2
2
40 rn
that gives
m
En = 2
2~
e2
40
2
1
,
n2
n = 1, 2, 3, . . . .
(1.37)
The integer n determines the energy of the bound state of the atom and
it is called principal quantum number. Figure 1.7 presents the diagram of
energy levels for the hydrogen atom. The state of minimum energy, called
ground-state, has the energy
2 2
e
m
13.6 eV .
(1.38)
E1 = 2
2~ 40
This value sets the scale for atomic energy. The states of higher energy are
called excited states. All energies of the bound atom are negative; states of
positive energies refers to the ionized atom.
The ionization energy of the hydrogen atom, defined as the amount of
energy required to force the electron from its lowest energy level entirely out
of the atom is
(1.39)
EI = E1 13.6 eV .
Let us now calculate the frequencies of the hydrogen spectrum. In the

transition between the states n1 and n2 > n1 , the frequency of the radiation
emitted or absorbed is
n1 n2 = (En2 En1 )/h
and the calculus yields
n1 n2
2 2

m
1
e
1
=
.
4~3 40
n21 n22
The wavelength n1 n2 = c/n1 n2 of the radiation is given by

2 2

1
m
e
1
1
1
1
=
= R 2 2 ,
n1 n2
4c~3 40
n21 n22
n1 n2
(1.40)
(1.41)
18
where
R =
2 2
m
e
1.097 107 m1
4c~3 40
(1.42)
is the Rydberg constant for hydrogen; the subscript reminds us the premise
that the nucleus is exceedingly massive compared with the electron.
The great success of the Bohr model had been in explaining the spectra of
hydrogen-like (single electron around a positive nucleus) atoms. Even though
the Bohr theory is now extended and altered in some essential respects by
quantum mechanics, its knowledge considerably helps the understanding of
new theories. In fact, a number of phenomena in spectroscopy can be dealt
with by making use of Bohr theory alone.
1.7
Correspondence principle
One of the guiding principles used in the development of quantum theory

was Bohrs correspondence principle (1920) which indicates that quantum
theory should give results that approach the classical physics results for large
quantum numbers.
To illustrate this principle let us discuss the hydrogen atom spectrum.
The quantum description of the atom is performed in the Bohr theory framework. By use of Eq. (1.40) the frequency of the radiation in the transition
between states n 1 and n is
n1,n
2 2

2 2
e
1
m
e
2n 1
m
1
=
2 =
.
3
2
3
2
4~ 40
(n 1)
n
4~ 40 n (n 1)2
We consider now large quantum numbers, i.e., n 1 . The frequency of the

quantum transition becomes
n1,n
2 2
2 2
m
e
2n
m
e
1
=
.
4~3 40 n4
2~3 40 n3
On the other hand the motion of the electron on the nth orbit has the
frequency
2 2
e
vn
m
1
n =
=
,
3
2rn
2~ 40
n3
where Eqs. (1.33) and (1.34) were used. According to classical theory the
atom emits radiation at the frequency n ; the comparison of the frequency
expressions gives n1,n n in agreement to the correspondence principle.
1.7 Correspondence principle
19
E/eV
0.00
Ionized atom
5
4
656.3 nm
486.1 nm
434.0 nm
410.2 nm
1875 nm
1282 nm
? ?
? ? ? ? Paschen series
Balmer series
3.40
121.6 nm
102.6 nm
97.3 nm
95.0 nm
0.54
? ?
0.85
Brackett series
1.51
? ? ? ?
Lyman series
13.6
Fig. 1.7 Energy level diagram for hydrogen and a few spectral lines of the Lyman,
Balmer, and Paschen series.
20
More that that, for large values of the quantum number n the hydrogen energy levels lie so close together that they form almost a continuum; it follows
that the classical continuum description of the spectrum should correspond
to transitions between two such states.
1.8
Einsteins phenomenological theory of radiation processes
In 1917 Einstein explained phenomenologically the radiation-matter interaction based on the quantum ideas of that time: Plancks quantum hypothesis and Bohrs planetary model of the hydrogen atom. Einsteins postulates could all be justified by the later developed quantum mechanical
treatments of the interaction processes.
Suppose N identical atoms in unit volume, each atom having a pair of
bound-state energy levels E1 and E2 , E2 > E1 (Fig. 1.8). The two atomic
levels are allowed to be multiplets with degeneracies g1 and g2 . The mean
numbers of atoms per unit volume in the two multiplet states are denoted
by N1 and N2 . Assuming that all the atoms are in these states,
N1 + N2 = N .
(1.43)
The atomic medium is considered in a radiation field whose spectral

radiant energy density at frequency given by
h = E2 E1
(1.44)
is () .
Einstein considers three basic interaction processes between radiation
and atoms (Fig. 1.8).
1. Spontaneous emission
An atom in state 2 spontaneously performes a transition to state 1 and
a photon of frequency is emitted. The photon is emitted in a random
direction with arbitrary polarization. The probability per unit time for occurence of this process is denoted by A21 and is called Einstein coefficient
for spontaneous emission.
The total rate of spontaneous emissions is
N 2 (t) = A21 N2 (t)
1.8 Einsteins phenomenological theory of radiation processes

6
E2 , g2 , N2
B12 ()
A21
?
Spontaneous
emission
21
B21 ()
?
Stimulated
emission
Absorption
E1 , g1 , N1
Fig. 1.8 Radiative transitions between to energy levels.

Table 1.2 Transition probability A for hydrogen lines in the visible range [10].
Each transition is identified by the wavelength and the statistical weights gi and
gk , of the lower (i) and upper (k) states.
/nm
410.173
434.046
486.132
656.280
gi
8
8
8
8
gk
72
50
32
18
A/s1
9.732 105
2.530 106
8.419 106
4.410 107
and the integration with the initial condition at t = 0 gives

N2 (t) = N2 (0) exp(A21 t) .
The time in which the population falls to 1/e of its initial value is
21 = 1/A21
(1.45)
and is called lifetime of level 2 with respect to the spontaneous transition to

level 1 (see Problem 1.16).
A few values of the transition probability rate are provided by Table 1.2.
In the absence of a radiation field the transition 1 2 is impossible due to
violation of the energy conservation law.
2. Absorption
In the presence of a radiation field an atom initially in state 1 can jump to
state 2 by absorption of a photon of frequency . The probability per unit
time for this process is assumed to be proportional to the spectral energy
density at frequency ; the total rate of absorptions is
N 1 = B12 ()N1 ,
(1.46)
22
where B12 is called Einstein coefficient for absorption.

3. Stimulated emission
Einstein postulates that the presence of a radiation field can also stimulate
the transition 2 1 of the atom; energy conservation law asks for the
emission of a photon of frequency . The probability per unit time for
this process is assumed to be proportional to the spectral energy density at
frequency ; the total rate of stimulated emissions is
N 2 = B21 ()N2 ,
(1.47)
where B21 is called Einstein coefficient for stimulated emission. The radiation produced during the stimulated emission process adds coherently to the
existing one; this means that radiation created through stimulated emission
has the same frequency, direction of propagation, polarization and phase as
the radiation that forces the emission process.
The stimulated emission process was unknown before 1917. The reason for
its introduction by Einstein will be made clear during next section.
Einstein coefficients defined above are independent of the radiation field
properties and are treated here as phenomenological parameters. They depend only on the properties of the two atomic states.
Due to all radiative transitions presented above, the populations N1,2 of
the two energy levels change in time according to the equations
N 1 = N 2 = B12 () N1 + [A21 + B21 ()]N2 ,
1.8.1
N1 + N2 = N . (1.48)
Relations between Einstein coefficients
Let us consider the atomic system defined above in equilibrium with

thermal radiation; the spectral radiant energy density () is given now
by Plancks formula [Eq. (1.9)]. This special case will lead us to establish
relations between Einstein coefficients.
The equilibrium condition for the radiation-matter interaction expresses
as follows. For the radiation field the equilibrium condition means equality of
emitted quanta and absorbed quanta. For the atomic system, the equilibrium
condition writes N 1 = N 2 = 0 . These conditions are equivalent. From
Eq. (1.48) at equilibrium,
B12 (, T )N1 + [A21 + B21 (, T )]N2 = 0 ,
1.8 Einsteins phenomenological theory of radiation processes
23
the spectral energy density of the thermal field can be expressed as

(, T ) =
A21 /B21
.
(B12 /B21 )(N1 /N2 ) 1
In thermal equilibrium, atomic energy levels are occupied according to the

MaxwellBoltzmann statistics. In exact terms the ratio of the population
densities of the two levels is
N1 /N2 = (g1 /g2 ) exp[(E1 E2 )/kB T ] = (g1 /g2 ) exp(h/kB T ) .
The use of this ratio into the expression of (, T ) gives
(, T ) =
A21 /B21
.
(g1 B12 /g2 B21 ) exp(h/kB T ) 1
(1.49)
This formula should be Plancks radiation formula (1.9), so

g1 B12 = g2 B21
(1.50a)
and
8 2
A21
= 3 h .
B21
c
(1.50b)
Relations (1.50) are known as Einsteins relations. These relations permit

to express the transition rates between a pair of levels in terms of a single
Einstein coefficient.
1.8.2
Spontaneous emission and stimulated emission as competing processes
An atom in an excited state can jump to a lower energy state through a

spontaneous emission or a stimulated one. Which process is most likely?
To ask this question, we consider the ratio R of the stimulated emission
rate and spontaneous emission one. This ratio is
R=
B21 ()
A21
and is dependent on the radiation field and frequency.

To be more specific, let us consider the thermal radiation field. The use
of Plancks radiation formula and the second Einstein equation gives
R=
1
.
exp(h/kB T ) 1
24
0
10
20
10
R
Fig. 1.9 Ratio of stimulated emission probability and spontaneous

emission probability for a two-level
atom in a thermal radiation field of
temperature T = 300 K.
40
10
60
10
10
10
11
10
12
13
10
10
(Hz)
14
10
15
10
For numerical evaluations we choose a typical temperature T = 300 K. The

ratio is R = 1 for = (kB T /h) ln 2 4.331012 Hz ( 69.2 m) in infrared
region. The dependence R versus frequency is presented in Fig. 1.9.
In the microwave region, for example at = 1010 Hz, R 624, so
the stimulated emission in more likely than the spontaneous emission.
For smaller frequencies spontaneous emission becomes negligible with
respect to stimulated emission.
In the near-infrared and visible region the ratio R takes on very small
values, so the spontaneous emission is the dominant process.
Can stimulated emission dominate over spontaneous emission for a conventional source of visible radiation? It can be proven that the spectral
energy density of a spectroscopic lamp is not sufficient to ensure a ratio
R > 1 . The stimulated emission dominates over spontaneous for a laser.
1.9
Experimental confirmation of stationary states
The idea of stationary states had been introduced to explain the discrete
spectrum of atomic systems. The first experimental confirmation of this
hypothesis was provided by James Franck and Gustav Hertz (1914). Their
experimental set-up is presented schematically in Fig. 1.10. Electrons emitted from a hot cathode C are accelerated toward the mesh grid G through a
low pressure gas of Hg vapour by means of an adjustable voltage U . Between
the grid and the anode A a small retarding voltage U 0.5 V is applied
1.9 Experimental confirmation of stationary states

C
Hg vapour
A
U

25
Fig. 1.10 Franck-Hertz set-up.
Current
Fig. 1.11
Current through a tube of
Hg vapor versus accelerating voltage in the
FranckHertz experiment.
5
10
15
Accelerating voltage, V
so that only those electrons above an energy threshold (eU ) will reach it.
The anodic current as a function of voltage (Fig. 1.11) does not increase
monotonically, as would be the case for a vacuum tube, but rather displays
a series of peaks at multiples of 4.9 V.
The experimental result is explained in terms of electronmercury atom
collisions. Due to the interaction between electron and atom, there is an
exchange of energy. Let us denote E1 and E2 the energy of the atom in
its ground state and first excited state, respectively. The minimum kinetic
energy of the electron for the atom excitation is practically E2 E1 (see
Problem 1.14).
If U < 4.9 V, an electron has not sufficient kinetic energy to excite a
mercury atom in a collision. The collision is elastic (i.e., the kinetic
energy is conserved) and the electron moves through the vapor losing
energy very slowly (see Problem 1.15). The current through the tube
increases with rising the accelerating voltage.
For 4.9 V < U < 4.9 V + U , in an electronmercury atom collision
the electron can transfer the energy E2 E1 = 4.9 eV to the mercury
atom; such an electron can not reach the anode, therefore the anodic
current shows a decrease.3
3
If there was no countervoltage applied, all electrons would reach the anode and the
26
Further increase in the accelerating voltage gives rise to an increase in

current. If the voltage is more than twice 4.9 V, the electron is able
to regain 4.9 eV of kinetic energy and cause a second excitation event
before reaching the anode. This explains the sequence of peaks.
From spectroscopy, mercury vapor, when excited, emits radiation whose
wavelength is = 253.7 nm; the energy of the corresponding photons is
hc/ 4.9 eV. Radiation of this wavelength is observed in Franck and
Hertz experiment. Thus this experiment is one of the most striking proofs
of the existence of stationary states.
1.10
Waveparticle duality of matter
The dual nature of radiation, wave and particle, was treated in Sect. 1.3.
In 1924 Louis de Broglie put forward the following hypothesis: material
particles, just like photons, can have a wavelike behaviour. One therefore
associates with a material particle of energy E and momentum p, a wave
characterized by the angular frequency and the wavevector k; the wave
characteristics are related to the particle ones by the same relations as for
photons [see Eq. (1.20)],
= E/~
and k = p/~ .
(1.51)
The corresponding wavelength,

= 2/k = h/p ,
(1.52)
is called de Broglie wavelength.

He argued that the stationary states of the electrons in the atom should
be such that there is an integral number of wavelengths around the orbit.
There was no experimental evidence for the matter waves in 1924. In
support of his hypothesis, de Broglie showed how Bohrs quantization rule
[Eq. (1.31)] could be derived from this hypothesis. Let us suppose that
the electron moves in a circular orbit of radius r with velocity v. De Broglie
argued that, if this is to be a stable stationary state, the wave associated with
the electron must be a standing wave (see Fig. 1.12). This requirement is
fulfilled if the circumference 2r contains an integral number n (n = 1, 2, . . .)
of electron wavelengths:
2r = n = nh/p = nh/mv .
current would increase monotonically.
1.10 Waveparticle duality of matter
27
rn
Fig. 1.12 Standing-wave pattern for an electron
wave in the n = 5 stationary state of hydrogen.
The equation can be rearranged to give mvr = n~ , i.e., the Bohr quantization condition.
Let us discuss on the experimental confirmation of the matter waves.
We expect interference and diffraction effects with matter waves when these
waves pass through apertures or slits with dimensions comparable with the
de Broglie wavelength. For a macroscopic particle of say, m = 1 kg and
speed v = 1 m/s , the de Broglie wavelength is 6.6 1034 m , which is
many orders of magnitude smaller than any imaginable aperture. To reach
much larger de Broglie wavelengths, waves associated to microparticles will
be investigated. If electrons are considered, the de Broglie wavelength of a
non-relativistic electron of energy E = p2 /2m is
=
h
1.23
p
nm .
2mE
E/eV
(1.53)
From this equation we immediately see that the de Broglie wavelength associated with electrons of energy 1 eV , 100 eV , and 10 keV are 1.23 nm ,
0.123 nm , and 0.0123 nm , respectively.4 As these wavelengths are comparable with the spacing of atoms in a crystal lattice, electrons with energies in
the eV to keV range are expected to be diffracted by crystal lattices. This
idea was confirmed experimentally in 1927 by Clinton Davisson and Lester
Germer, and independently by George Paget Thomson.
1.10.1
DavissonGermer experiment
The experimental arrangement used by Davisson and Germer is schematically shown in Fig. 1.13. The tungsten filament F is heated by a low voltage
4
Electrons with these energies are obtained by accelerating them through a potential
difference of 1 V, 100 V, and 10 kV, respectively.
28
U

F
A
Fig. 1.13 Outline of the experimental

arrangement in the electron diffraction
experiments of Davisson and Germer.
Incident
electron ?
beam
*
Scattered
beam
power supply and emits electrons. These electrons are then accelerated in
the adjustable potential difference U towards the anode A; at the exit of
the electron gun, the electrons possess the kinetic energy E = eU . The
collimated electron beam is directed normally against a target C cut from a
single crystal of nickel. The electrons are scattered in all directions by the
atoms of the crystal; the intensity of the beam in the direction is measured
by the electron detector D which is connected to a sensitive galvanometer.
By rotating the detector D, the dependence of the intensity of the scattered beam on the scattering angle can be investigated. The apparatus is
enclosed in a vacuum chamber.
For a given voltage U , the intensity versus scattering angle plot shows a
peak. The experimental result is similar to that in case of x-rays scattered
by a crystal surface. Hence, the existence of the maximum proves qualitatively the de Broglie hypothesis. To derive the condition for constructive
interference, the crystal is regarded as being composed of a set of parallel
planes which contain all of the atoms in the crystal (see Fig. 1.14). A part
of the incident electron wave is reflected by each of the planes. The reflected
waves interfere and a maximum is obtained when the scattered waves from
adjacent planes are in phase, i.e., the path difference is an integral number
of wavelengths.
Figure 1.15 shows the scattering of the rays I and II by two adjacent
planes. The rays are incident at the angle to the planes of the crystal and
then reflected at this same angle; the angle is related by the angle by
= /2 /2 . Ray II travels a longer path than ray I; this difference in
path is M N + N P = 2d sin . The condition for constructive interference is
1.10 Waveparticle duality of matter
29
Incident beam
??????
d
Scattered
>
>
Fig. 1.14 The scattering of electron wave
>
beam
>
by a crystal is interpreted as reflection on
>
>
a series of parallel atomic planes followed
Crystal by the interference of the reflected waves.
is the angle between the incident wave and
an atomic plane and d is the the distance
I
Atomic
between two adjacent atomic planes.
planes
thus
2d sin = n ,
n = integer,
(1.54)
which is known as the Bragg equation. By use of the distance D between

atoms, the distance between the atomic planes can be expressed in the form
d = D cos .
The Bragg condition becomes now
D sin 2 = n ,
n = integer,
or, in terms of the scattering angle ,

D sin = n ,
n = integer.
(1.55)
Davisson and Germer verified the validity of this condition for the scattering of an electron beam on a nickel crystal; the atomic spacing D =
2.15 1010 m was known from x-rays diffraction experiments. Davisson
and Germer found that for the accelarating voltage U = 54 V the maximum intensity is observed in the direction = 50 . Assuming a first-order
diffraction maximum (n = 1), Eq. (1.55) gives the wavelength
= 2.15 1010 m sin 50 1.65 1010 m .
On the other hand, the de Broglie wavelength of a 54 eV electron calculated from Eq. (1.53) gives 1.67 1010 m , which agrees with the value
of 1.65 1010 m , within the limits of experimental error. Similar measurements were performed at other accelerating voltages and the agreement
between the wavelength calculated based on the Bragg condition and that
calculated based on the de Broglie relation is maintained.
30
?
II
?
I
>I
> II
M
d
Atom
Atomic planes
Fig. 1.15 Derivation of the Bragg equation.
1.11
Heisenberg uncertainty principle
An interesting interpretation of the wave-particle duality of all physical

entities has been given by Werner Heisenberg (1927). The uncertainty principle, or indeterminacy principle, refers to the simultaneous measurement of
the position and the momentum of a particle and states that the uncertainty
x involved in the measurement of a coordonate of the particle and the uncertainty px involved in the measurement of the momentum in the same
direction are related by the relationship
x px ~/2 .
(1.56)
To illustrate the uncertainty principle, we consider a thought experiment.

Suppose a parallel beam of monoenergetic electrons that passes through a
narrow slit and is then recorded on a photographic plate (Fig. 1.16). The
precision with which we know the y-position of an electron is determined
by the size of the slit; if d is the width of the slit, the uncertainty of the
y-position is y d . Reducing the width of the slit, a diffraction pattern is
observed on the photographic plate. The wavelength of the wave associated
to the electrons is given by Eq. (1.52), where p designates the momentum
of the electrons. The uncertainty in the knowledge of the y-component of
electron momentum after passing through the slit is determined by the angle
corresponding to the central maximum of the diffraction pattern; according
1.11 Heisenberg uncertainty principle
31
y
6
Incoming
beam- 6
- d
- ?
Screen with
a single slit
Observing
screen
Fig. 1.16 Diffraction through a single slit.
to the theory of the diffraction produced by a rectangular slit, the angle is

given by d sin = . We have
py p sin = p
h
=
d
d
and
h
= h,
d
in agreement with Eq. (1.56). Note that:
y py d
To reduce the uncertainty in the determination of the coordinate y

of the particle, a narrower slit is required. This slit produces a wider
central maximum in the diffraction pattern, i.e., a larger uncertainty in
the determination of the y-component of the momentum of the particle.
To improve the precision in the determination of the y-component of
the momentum of the particle, the width of the central maximum in
the diffraction pattern must be reduced. This requires a larger slit,
which means a larger uncertainty in the y-coordinate of the particle.
It is common to consider in everyday life that a measurement can be
performed without changing the state of the physical system. The above example clearly shows that in contrast to the classical situation, at the atomic
level, measurement inevitably introduces a significant perturbation in the system.
The uncertainty principle implies that the concept of trajectory for particles of atomic dimensions is meaningless. It follows that for such particles
the description of the motion needs a different picture.
32
For everyday macroscopic objects the uncertainty principle plays a negligible role in limiting the accuracy of measurements, because the uncertainties
implied by this principle are too small to be observed.
1.11.1
Uncertainty relation and the Bohr orbits
In Sect. 1.6 the electron of the hydrogen atom is supposed in a circular

motion around the nucleus. Let us investigate the compatibility of this
picture with the uncertainty relation [Eq. (1.56)].
The classical treatment of the electron motion is justified for small uncertainties in the position and momentum,
x r
from which we infer
and px p ,
x px
1.
r
p
(1.57)
(1.58)
For the motion on the Bohr orbit n , the quantization rule gives pr = n~ .
The use of Heisenberg uncertainty relation yields
x px
1
.
r
p
2n
It is clear now that this result is in contradiction with Eq. (1.58) for small
values of the quantum number n . It follows that the classical motion picture
of the electron on circular orbits must be rejected.
1.12
Questions and problems
1.1 Does a blackbody always appear black?

1.2 Explain the cooling of Earth surface at night. When is the Earth
surface coldest?
1.3 Determine the number of photons emitted per second by a P = 2 mW
He-Ne laser operating on the wavelength = 632.8 nm.
Solution. The energy of a photon is hc/ . The number of photons emitted per
second is
P
6.37 1015 photons/s .
hc/
1.12 Questions and problems
33
1.4 In a television tube, electrons are accelerated by a potential difference

of 25 kV. Determine the minimum wavelength of the x-rays produced when
the electrons are stopped at the screen.
Solution. The energy acquired by an electron accelerated by the potential difference U = 25 kV is E = eU . This energy may be radiated as a result of electron
stopping; the minimum wavelength radiated is obtained when all energy is radiated
as a single photon:
min = hc/E = hc/eU 5.0 1011 m = 50 pm .
Almost all of this radiation is blocked by the thick leaded glass in the screen.
1.5 The temperature of a person skin is skin = 35 C .

(a) Determine the wavelength at which the radiation emitted from the
skin reaches its peak.
(b) Estimate the net loss of power by the body in an environment of
temperature environment = 20 C . The human skin has the emittance =
0.98 in infrared and the surface area of a typical person can be estimated as
A = 2 m2 .
(c) Estimate the net loss of energy during one day. Express the result in
calories by use of the conversion relation 1 cal = 4.184 J .
Solution. (a) By use of Eq. (1.4),
max =
b
Tskin
9.5 m .
This wavelength is in the infrared region of the spectrum.

(b) The power emitted by the body is [see Eq. (1.3)]
4
Pemitted = Tskin
A 974 W ,
while the power absorbed from the environment is

4
Pabsorbed = Tenvironment
A 819 W .
The net outward flow of energy is

P = Pemitted Pabsorbed 155 W .
(c) The net loss of energy in a time t = 24 3 600 s is E = P t 3 207 kcal.
The result is an overestimation of the real net loss of energy, because the clothes
we wear contribute to a significant reduction of the skin emittance.
34
1.6 Prove that the relation between radiant exitance M of a blackbody and
the energy density of the blackbody cavity is
M = (1/4)c .
(1.59)
Solution. Let us consider a small surface of the body; this can be considered as
plane. Let us denote by A the area. We choose a 3-D Cartesian coordinate system
with the origin O on the emitting surface and the Oz-axis perpendicular to the
surface and directed outward (see figure below).
z
6 n

A
R O
c t
We first write the flux of energy through the surface of area

A inside the solid angle d = sin d d around the direction n determined by polar angles and . During the time
interval t , the energy emitted inside the solid angle d is
located inside the cylinder of generatrix paralell to n and
length c t . The energy inside this volume is Ac t cos
and only the fraction d/4 propagates in the considered
solid angle.
The total energy emitted through the surface of area A in the time interval t
is
Z
=/2Z =2
=0
Ac t cos
=0
1
sin d d
= cA t.
4
4
It follows that the energy emitted in unit time by unit area is given by Eq. (1.59).
Remark. In case we are interested in the relation between the spectral quantities
M and , we restrict ourselves to the radiation in the wavelength interval (, +
d). The energy emitted with the wavelength in the specified interval in t is
Z =/2Z =2
sin d d
1
d Ac t cos
= c d A t.
4
4
=0
=0
The energy emitted in unit time through the unit area of surface is
E d = (1/4)c d
from which Eq. (1.5) is inferred.
1.7 Derive Wiens displacement law from Eq. (1.10).

Solution.

40hc
exp(hc/kB T )
1 hc
hc
d
() =
1 +
+ exp
.
d
6 [exp(hc/kB T ) 1]2
5 kB T
kB T
The condition d ()/d = 0 yields the transcendental equation
1 x/5 = exp(x) ,
where the shorthand notation x = hc/kB T have been used. Besides the trivial
solution x = 0 , a positive solution exists, x 4.965 (see figure below).

1
35
Graphical solution of the equation

1 x/5 = exp(x) .
1 x/5
exp(x)
0
-x
The spectral energy density is maximum for the wavelength max given by
max T
hc
2.898 103 m K.
4.965 kB
1.8 A zinc plate is irradiated at a distance R = 1 m from a mercury lamp

that emits through a spectral filter P = 1 W radiation power at = 250 nm.
The penetration depth of the radiation is approximately equal to the radiation wavelength. In the classical model of radiation-matter interaction,
the radiation energy is equally shared by all free electrons. Calculate the
minimum irradiation time for an electron to accumulate sufficient energy to
escape from the metal. Free electron density in zinc is n = 1029 m3 and the
work function is = 4 eV.
Solution. In a time interval t the plate of area A receives the energy
A
Pt
4R2
and this is accumulated by the free electrons in the volume A . On the condition
that an electron acquires the energy ,
A
P t = nA .
4R2
The minimum irradiation time is
t=
4R2 n
2.0 105 s
P
in strong contradiction to the experimental results.
1.9 Blue light of wavelength = 456 nm and power P = 1 mW is incident

on a photosensitive surface of cesium. The electron work function of cesium
is = 1.95 eV.
36
(a) Determine the maximum velocity of the emitted electrons and the
stopping voltage.
(b) If the quantum efficiency of the surface is = 0.5 %, determine the
magnitude of the photocurrent. The quantum efficiency is defined as the
ratio of the number of photoelectrons to that of incident photons.
Solution. (a) The threshold wavelength of the photoelectric effect for cesium is
0 = hc/ 636 nm < ,
so electrons are extracted from cesium.
To calculate the maximum velocity of the photoelectrons, we make use of
Eq. (1.14), where = c/ . We get vmax 5.2 105 m s1 . As vmax /c 1,
the nonrelativistic expression of the kinetic energy proves to be justified.
The stopping voltage is given by Eq. (1.16), where = c/ . We get U0
0.77 V.
(b) The number of electrons extracted in unit time is
n=
P
hc/
forming a current of magnitude

I = ne =
eP
1.8 A .
hc
1.10 Prove that a free electron cannot absorb a photon.

Solution. The collision between the photon and the electron is investigated in
their centre of mass reference frame, i.e., the frame of reference in which the total
momentum is zero. The hypothetical process is presented below. Here, p denote
the magnitude of the momentum of the electron and photon.
p
::::-
p

Before absorption
After absorption
Let
p us denote by me the electron mass. The initial energy of the system is
pc + m2e c4 + p2 c2 , while the energy of the final state is me c2 . It is clear that
conservation of energy is violated, so the process cannot occur.
Remark. An electron participating in the photoelectric effect is not free, but
bound to either an atom, molecule, or a solid. The electron and the heavy matter
to which the electron is coupled share the energy and momentum absorbed and it is
always possible to satisfy both momentum and energy conservation. However, this
heavy matter carries only a very small fraction of the photon energy, so that it is
usually not considered at all.
37
1.11 X-rays of wavelength 70.7 pm are scattered from a graphite block.

(a) Determine the energy of a photon.
(b) Determine the shift in the wavelength for radiation leaving the block
at an angle of 90 from the direction of the incident beam.
(c) Determine the direction of maximum shift in wavelength and the
magnitude of this shift.
(d) Determine the maximum shift in the wavelength for radiation scattered by an electron tightly bound to its carbon atom.
Solution. (a) E = hc/ 2.81 1015 J 1.75 104 eV .
Remark. This energy is several orders of magnitude larger than the binding
energy of the outer carbon electrons, so treating these electrons as free particles in
the Compton effect is a good approximation.
(b) By making use of Eq. (1.21), we get = 2.43 pm.
(c) The direction of maximum shift in wavelength is = , i.e., the photon is
scattered backwards; ()max = 2C 4.85 pm.
(d) The photon collides with the entire atom whose mass is 12 u . Compton
wavelength of the carbon atom is 1.111016 m. The maximum change of the
wavelength due to scattering is 2.221016 m, too small to be measured.
1.12 In a Compton scattering experiment (see Fig. 1.6) a photon of energy

E is scattered by a stationary electron through an angle .
(a) Determine the angle between the direction of the recoiling electron
and that of the incident photon.
(b) Determine the kinetic energy of the recoiling electron.
Solution. (a) Given that p is the momentum of the incident photon and p and pe
the momenta of scattered photon and electron after the collision, the conservation
of momentum requires that
pe = p p .
This relation is projected on two perpendicular axes shown in the figure:
h
h
cos ,

h
pe sin = sin .
pe cos =
Dividing side by side the two equations we get

cot =
cot .
sin
By use of Eq. (1.21), the angle is given by

C
cot = 1 +
tan = 1 +
tan .
2
mc2
2
38
y
6
p*
p-
-x
Momentum conservation in the Compton effect

and the choice of a xOy coordinate system.
pR
e
(b) The kinetic energy of the recoiling electron is equal to the energy loss of the
photon:
T =
hc hc
hc C (1 cos )
(E/mc2 )(1 cos )
=
=
E.
+ C (1 cos )
1 + (E/mc2 )(1 cos )
1.13 Use position-momentum uncertainty relation to estimate the dimensions and the energy of the hydrogen atom in its ground state.
Solution. Let the electron be confined to a region of linear dimension r . We
estimate the energy of the atom.
The potential energy of the electron is of the order of
hV i =
e2
.
40 r
According to the uncertainty principle, the uncertainty p in its momentum

is p ~/r . The average kinetic energy of the electron is hT i = (1/2m)hp2 i and
assuming a zero average momentum we get
hT i =
1
~2
(p)2
.
2m
2mr2
The total energy of the atom is

E = hT i + hV i
Let us denote
Emin (r) =
~2
e2
.
2mr2
40 r
~2
e2
.
2
2mr
40 r
The atom settles to a state of lowest energy. Notice that for large r
values, the potential energy dominates; it follows that expanding the atom
increases the total energy. However, for small enough r, the kinetic energy is
the dominant contribution and the total energy lowers as the atom expands.
39
It follows that there must exists a value of r for which the total energy is a
minimum. We have

40 ~2
dEmin
~2
e2
e2
= 3 +
r
.
=
dr
mr
40 r 3
40 r 3
me2
The energy attains indeed a minimum for r = 40 ~2/me2 = a0 . The total energy for this radius is exactly the energy of the ground state of the
hydrogen atom [see Eq. (1.38)].
It should be pointed out that the Heisenberg uncertainty relation can
be used to give only an order of magnitude of the hydrogen atom size or
its ground state energy. The exact quantitative agreement is accidental. In
fact, we had intentionally chosen the lower bound value in the Heisenberg
uncertainty relation in such a way (i.e., ~) that the resulting ground state
energy is exact.
1.14 An electron is bombarding an atom at rest in its ground state of energy
E1 . Prove that the threshold kinetic energy of the electron, required for the
atom excitation to the first excited state of energy E2 , is approximately
equal to E2 E1 .
Solution. Let us denote m and M the mass of the electron and the atom, respectively. We have
m
m
1
.
M
MH
1836
The threshold condition for the excitation of the atom as a result of the collision
will be expressed in the centre of mass (CM) frame of reference: all kinetic energy
of the system is used for the atom excitation. In other words, in the CM frame of
reference, the electron and the atom are both at rest after the collision.
We denote p and P the initial momentum of the electron and the atom in the
CM frame of reference, respectively. The conservation of momentum and energy in
the CM frame of reference gives
p+P =0
and
1 2
1 2
p +
P + E1 = E2 .
2m
2M
Combining these equations we get

p2 =
2M m
(E2 E1 ) .
M +m
The initial velocities of the particles with respect to the CM frame of reference
are
v=
p
m
and V =
P
p
= .
M
M
40
The initial velocity of the electron with respect to the atom is

1
1
+
p.
vV =
m M
The sought kinetic energy is
T =
1
(M + m)2 2
m
m(v V )2 =
p = 1+
(E2 E1 ) E2 E1 .
2
2
2M m
M
1.15 Show that the change in kinetic energy of a particle of mass m, with
initial kinetic energy T , when it collides with a particle of mass M initially
at rest in the laboratory frame of reference is
T =
4M/m
T.
(1 + M/m)2
Discuss the case M m .

Solution. Let us designate the velocity of the projectile in the laboratory frame of
reference by v. We choose an axis with the orientation of v. The conservation of
momentum and energy gives
mv = mv + M V
and
1
1
1
mv 2 = mv 2 + M V 2 ,
2
2
2
where v and V denote the final velocity of particle m and M , respectively. Arranging the two equations in the form
m(v v ) = M V
and m(v v )(v + v ) = M V 2 ,
first degree equations are obtained:

v v = (M/m)V
and v + v = V .
The velocity of particle M after the collision is

V =
2
v.
1 + M/m
The change in the kinetic energy of the projectile m is

1
4M/m
T = M V 2 =
T
2
(1 + M/m)2
For M m we have
|T |
4M/m
m
=4
1.
T
(M/m)2
M
41
1.16 Justify the name of lifetime for the time interval defined by = 1/A
[see Eq. (1.45)].
Solution. We calculate the average time spent by the atom before de-excitation.
Suppose at t = 0 there are N (0) atoms in the upper energy level. During the time
interval (t dt/2, t + dt/2), a number
AN (t) dt = AN (0) exp(At) dt
of atoms de-excite. These atoms have spent a time t in the upper energy level.
Thus, the probability that an atom remains in the upper energy level a time t is
AN (t) dt
= A exp(At) dt .
N (0)
The average time spent by an atom in the upper energy level is
Z
Z

1
tA exp(At) dt = t exp(At)0 +
exp(At) dt =
=.
A
0
0
1.17 The wavepacket for a particle of mass m has the uncertainty x .

After what time the wavepacket will spread appreciably?
Solution. The uncertainty in the particle momentum is p ~/2x . The uncertainty in the particle velocity is then v = p/m ~/2mx . After a time
t the spreading of the wavepacket due to the uncertainty of its velocity is (v)t .
This spreading becomes important when it is of the same order of magnitude as the
initial spreading, x . We define the spreading time ts by (v)ts = x . It results
ts =
2m(x)2
x
.
v
~
1.18 The wavelength associated to a particle is known up to , where

. Derive a formula for the uncertainty x in the particle position.
Solution. The uncertainty in the wavelength implies an uncertainty in the momentum

h
h
p =
2 .
The uncertainty in the particle position is

x
~/2
2
=
.
p
4
42
Chapter 2
Postulates of quantum
mechanics and applications
2.1
First postulate
Postulate 1 For a particle moving under the influence of an external potential, there is an associated wavefunction. That wavefunction determines
everything that can be known about the particle and is a single-valued function of the space coordinates and the time. In general, it is a complex
function whose squared modulus, evaluated at a particular point and time,
is proportional to the probability density of the particle at that point and
time.
2.2
Schr
odinger equation
In case of light, the interference pattern or diffraction one is explained

using waves of form
(r, t) = A exp[i(k r t)] .
(2.1)
We extend the treatment for the case of microparticles. For simplicity,

we consider the one-dimensional case. The expression of a wave of constant
kx and angular frequency is
(x, t) = A exp[i(kx x t)] .
(2.2)
In case of microparticles,
kx =
px
~
and =
E
p2
= x ,
~
2m~
(2.3)

i
i
p2x
(x, t) = A exp (px x Et) = A exp (px x
t) .
(2.4)
~
~
2m
44
We have
= E ,
t
~
i
= px ,
x
~
Combining these equations,
i~
p2
= E = x ,
t
2m
(2.5)
2
1
= 2 p2x .
x2
~
(2.6)
i~
~2 2
.
=
t
2m x2
(2.7)
As the differential equation is linear and homogeneous, the general solution is

Z
i
(x, t) =
A(px ) exp (px x E(px )t) dpx .
(2.8)
~
Equation (2.7) is called the Schr

odinger equation for the free particle,
in the one-dimensional case. Let us extend the equation for the non-free
particle. We do this for the case of a force Fx deriving from a potential
energy V (x, t):
Fx = V (x, t) .
(2.9)
x
The energy of the particle is now given by
E = p2x /2m + V (x, t) .
(2.10)
How the extend Eq. (2.7)? We associate operators to the dynamical

variables E and px of the particle:
= i~
E
t
and px = i~
.
x
(2.11)
By writing Eq. (2.7) in the form

= T
E
where
T = p2x /2m
(2.12)
is the kinetic energy operator, the natural extension of the equation is

= (T + V ) .
E
2.3 Probability conservation
45
We take V = V . The 1D-Schr

odinger equation for a particle in a potential
field is now
~2 2
i~ =
+ V (x, t) .
(2.13)
t
2m x2
The extension to the three-dimensional case is
i~
~2 2
(r, t) =
(r, t) + V (r, t) (r, t) .
t
2m
(2.14)
Postulate 2 The time evolution of the wavefunction is given by the timedependent Schr
odinger equation (TDSE).
2.3
Probability conservation
Consider the wavefunction (r) is normalized at some time t0 . The

wavefunction evolves in time according to the time-dependent Schr
odinger
equation. The probability interpretation of the wavefunction only makes
sense if the normalization condition remains satisfied at all subsequent times;
it is proven below that this is the case.
The probability
R of locating the particle within a volume V at time t is
proportional to V |(r, t)|2 d3 r . The rate of change of this quantity can be
calculated from the rate of change of as given by TDSE (2.14),
d
dt

|(r, t)| d r =
(r, t) (r, t) + (r, t) (r, t) d3 r
t
t
V
V
Z

i~
(r, t)2 (r, t) (r, t)2 (r, t) d3 r
=
2m V
Z
i~
=
[ (r, t)(r, t) (r, t) (r, t)] d3 r
2m V
Z
= j(r, t) d3 r , (2.15)
2
Z
where
j(r, t) = i
~
[ (r, t)(r, t) (r, t) (r, t)] .
2m
(2.16)
Applying the divergence theorem, which relates the volume integral of the
divergence of a vector to the surface integral of the vector,
Z
I
d
2 3
|(r, t)| d r = j(r, t) n dS ,
(2.17)
dt V
46
where is the bounding surface of V and n is the surfaces outward unit

normal.
If we extend the surface to infinity, the wavefunction must approach
zero to ensure the posibility of normalization; the surface integral must vanish,
Z
d
|(r, t)|2 d3 r = 0 ,
(2.18)
dt r
so the norm of the wavefunction does not change in time.
Let us analyze the physical content of Eq. (2.17). On the left side we
have the rate of change of the probability that the particle is located within
V. It follows that rhs can be interpreted as a current of probability and j
is the probability current density; this quantity is the analog of the current
density encountered in electricity. Now, Eq. (2.17) is the integral form of
the law of probability conservation.
Let us come back to Eq. (2.15) and arrange it as

Z
2
|(r, t)| + j(r, t) d3 r = 0 .
t
V
Since the volume V is arbitrary, the integrand must vanish everywhere:
P (r, t) + j(r, t) = 0 .
t
(2.19)
This is the continuity equation or the local law of probability conservation.

In one dimension, the probability current density (2.16) acquires the form

~

j(x, t) = i
(x, t) (x, t) (x, t) (x, t) .
(2.20)
2m
x
x
Let us calculate the probability current density for the free-particle wavefunction
(x, t) = A exp[i(px Et)/~] .
We have
j(x, t) = i

~
p|A|2
p|A|2
p
i
i
=
|A|2 .
2m
~
~
m
(2.21)
Thus, the probability current density is equal to the probability density |A|2
multiplied by the particle velocity p/m. This is analogous to electricity, in
which the current density is the charge density multiplied by the velocity of
charge carriers.
2.4 Constraints on the wavefunction
2.4
47
Constraints on the wavefunction
The probability amplitude interpretation of the wavefunction and its

time evolution equation imply some constraints on the wavefunction:
1. To guarantee a unambiguous value of probability of finding the particle
at a particular position and time, the quantity ||2 must be single valued.
The wavefunction may be a complex valued function, since it is only ||2
that has physical significance.
2. To ensure that the probability for finding the particle in any region of
space do not exceed unity, the wavefunction must be square integrable, i.e.,
Z
||2(r, t) d3 r < .
r
This implies that the wavefunction approaches zero at infinity. Sometimes

functions that violate this condition are used and Eq. gives one such function.
3. The wavefunction must be continuous everywhere.
4. For the existence of second spatial derivative, first derivative has to
be continuous (the wavefunction is smooth). This requirement can not be
fulfilled
Having set up these constraints on the wavefunction we are now ready
to consider the solutions to the Schr
odinger equation in some specific cases.
2.5
Time-independent Schr
odinger equation
Suppose the potential V does not have explicit time dependence. For
example, an electron in an atom experiences an electrostatic force directed
towards the nucleus; this force derive from a potential dependent only on
the distance between electron and nucleus. It is shown below that TDSE
can be simplified to a form not containing the time variable. the method of
separation of variables.
We look for a solution in the form of a product of spatial and temporal
terms,
(r, t) = u(r) T (t) .
(2.22)
This is substituted into the TDSE (2.14). After dividing both sides by
u(r) T (t) we get

1 d
1
~2 2
i~
T (t) =
u(r) + V (r) u(r) .

T (t) dt
u(r)
2m
48
Since the lhs depends only on t, and the rhs only on r, the only way this
equation can be true is if both sides equal a constant; as the dimension of
the constant is that of energy, the constant is denoted by E:

1 d
1
~2 2
T (t) = E and
u(r) + V (r) u(r) = E .

i~
T (t) dt
u(r)
2m
The first of these differential equations can be solved immediately,
T (t) = exp(iEt/~) .
(2.23)
The second equation, arranged as
~2 2
u(r) + V (r) u(r) = E u(r) ,
2m
(2.24)
is the time-independent Schr

odinger equation (TISE). Based on our previous
discussion on the individual terms of the TDSE, E is identified as the energy
of the system.
TISE is a linear second-order differential equation in which one has to
solve simultaneously for a set of energy values, E, and a set of corresponding
functions u(r). This equation is an eigenvalue one for the operator
~2 2
+ V (r)
H =
(2.25)
2m
called energy operator ; E is called energy eigenvalue, while u(r) is referred
to as energy eigenfunction (eigenstate). To each eigenvalue E it corresponds
one ore more eigenfunctions; in the latter case we say that the eigenvalue is
degenerate.
Let E be an energy eigenvalue and u(r) an energy eigenfunction for E;
the corresponding solution of TDSE is
(r, t) = u(r) exp(iEt/~) .
(2.26)
The time-dependence of this solution is contained entirely in an overall phase

with no physical implications; this property justifies the name of stationary
state for the state given by Eq. (2.26).
The general solution of TDSE is a linear combination of functions given
by Eq. (2.26).
For the one-dimensional problems, TISE (2.24) becomes
~2 d2
u(x) + V (x) u(x) = E u(x) .
2m dx2
(2.27)
Most of the effort in quantum mechanics goes into solving the TISE for
various systems; a few simple examples follow.
2.6 Potential wells
49
V (x)
6
Fig. 2.1 A one-dimensional potential well. The

classical motion of a particle of energy E takes
place in the coordinate interval [xmin , xmax ] .
xmin
2.6
x0
-x
xmax
Potential wells
There are many examples of particles whose motion is confined to a

limited region of space: electrons in metals, electrons in atoms, nucleons
in nuclei, and so on. The interaction between particles in such cases is
represented through a potential energy that possesses a local minimum. The
region surrounding the local minimum of potential energy is called potential
well.
Consider for simplicity the one-dimensional case (Fig. 2.1). Classically,
a particle having the potential energy V (x) is subjected to the force
Fx (x) =
d
V (x) .
dx
(2.28)
The force is zero for the local minimum position, x0 , i.e., this position is an
equilibrium one; if the particle is displaced from x0 , the force tends to bring
the particle back toward this position. The energy of the particle is E Vmin
and the motion takes place between the abscissas xmin and xmax determined
as solutions of the equation V (x) = E . It is said that the particle is in a
bound state.
Suppose now a potential which is bounded above and a particle of energy
E such that V (x) E for all x-values. The classical mechanics treatment of
the motion allows the particle to be found in whatever position on the axis;
the state of the particle is called unbound state.
50

V (x)
6
V (x) =
V (x) =
-x
Fig. 2.2 The infinitely deep one-dimensional square potential well of width a.
2.7
2.7.1
The one-dimensional infinite well

Introduction
Let us imagine a particle of mass m is moving freely inside a closed

tube of length a; collisions between the particle and the ends of the tube
are assumed to be elastic. Since the particle can not leave the tube, the
potential experienced by the particle can be approximated as
(
0
V (x) =
0xa
otherwise,
(2.29)
where the axis Ox is chosen with the origin at one end of the tube and
the other end is positioned at x = a (Fig. 2.2); the constant value of the
potential inside the tube is chosen V (x) = 0 . It is clear that real potentials
can not be infinite, nor can they change infinitely fast; the approximation is
justified for reasons of mathematical simplicity.
Classically, the particle inside such a well can be at rest or it bounces
back and forth due to ellastic collisions with the walls. The energy of the
particle is E = 0 in the first case and E > 0 in the latter. Whatever value
E > 0 is possible; we say that the particle has a continuous spectrum of
energy. For the moving particle, the probability per unit length of finding
the particle is constant inside the well and the normalization condition gives
Pcl (x) = 1/a .
(2.30)
2.7 The one-dimensional infinite well
2.7.2
51
Energy eigenvalues and eigenfunctions
In the quantum mechanical framework, we need to solve the one dimensional time-independent Schr
odinger equation (2.27) with the potential given
by Eq. (2.29).
In the regions x < 0 and x > 0 we have
~2 d2
u(x) + u(x) = E u(x)
2m dx2
and the only possible solution is u(x) = 0 which means that the probability
of finding the particle outside the well is zero.
In the interval [0, a] the time-independent equation is that of a free particle of zero potential energy,
~2 d2
u(x) = E u(x) ,
2m dx2
that can be expressed as

d2
2m
u(x) + 2 E u(x) = 0 .
dx2
~
(2.31)
The form of the solution depends on the sign of the energy.

Let us first look for negative energies. Defining = 2mE/~ the
solution is
u(x) = A exp(x) + B exp(x) ,
0 x a,
where A and B are constants that are to be determined. The solution

(
A exp(x) + B exp(x) 0 x a
u(x) =
0
otherwise,
must be a continuous function. Continuity of the wavefunction at the points
x = 0 and x = a gives
A + B = 0 and A exp(a) + B exp(a) = 0 .
The result is A = B = 0 , so u(x) = 0 everywhere. This is not an acceptable
wavefunction. We conclude that the particle can not have a negative energy.
The result is that expected as the energy is the sum of the kinetic energy, a
positive defined quantity, and the potential one which is also positive here.
52

Next we look for an energy E = 0 . The equation (2.31) has the solution
u(x) = Ax + B ,
0xa
and the continuity condition of the wavefunction

(
Ax + B 0 x a
u(x) =
0
otherwise,
gives B = 0 and Aa + B = 0 with the solution A = B = 0 . Again u(x) = 0
everywhere, i.e., a unacceptable solution. The result is that expected, as a
state of zero energy would imply an exact position determination and also
an exact value (zero) of the momentum in contradiction with the Heisenberg
uncertainty principle.
We turn now to searching for positive energies. Defining
k = 2mE/~ > 0 ,
(2.32)
Eq. (2.31) has the general solution
u(x) = A sin kx + B cos kx ,
0xa
and the wavefunction is

(
A sin kx + B cos kx
u(x) =
0
0xa
otherwise.
(2.33)
The continuity condition at x = 0 gives B = 0 . The same condition at

x = 0 reads A sin ka = 0 . Not to get u(x) = 0 everywhere, the condition
sin ka = 0 must be satisfied; this equation can be recognized as the condition
for a standing wave in the interval [0, a]. Since k > 0 the solution is
ka = n ,
n = 1, 2, . . . .
(2.34)
This means that the wavenumber k is quantized (takes on discrete values)

and can have only the particular values
kn = n/a ,
n = 1, 2, . . . .
(2.35)
Now, from Eq. (2.32) the energy of the particle is also quantized:
En =
2 ~2 2
n ,
2ma2
n = 1, 2, . . . .
(2.36)

E/E1
6
..
.
25
53
n
5
20
4
15
10
2
Ground state
Fig. 2.3 Energy level diagram for the particle in

the one-dimensional infinite well. In the ground
state (n = 1) the energy is positive.
The energy level diagram of the particle is shown in Fig. 2.3. Quantification
of the energy arises naturally by imposing boundary conditions on solutions
of Schr
odinger equation as opposed to its ad-hoc introduction in its model
of the hydrogen atom.
Normalization condition determines the value of the constant A:
Z
Z a
n
a
2
|u(x)| dx =
|An |2 sin2
x dx = |An |2 = 1
a
2
0
p
hence |An | = 2/a . Since the phase of the constant remains arbitrary, we
take the simpliest choice, i.e., arg An = 0 . The wavefunctions can now be
written in the final form
(p
2/a sin nx/a 0 x a
un (x) =
n = 1, 2, . . . .
(2.37)
0
otherwise,
The probability per unit length of finding the particle at x in a state n is
(
(2/a) sin2 nx/a 0 x a
Pn (x) = |un (x)|2 =
n = 1, 2, . . . . (2.38)
0
otherwise,
Figure 2.4 shows the plot of first few wavefunctions and probability densities.
In a plot of the probability density, the peaks correspond to positions of high
probability of finding the particle; the valleys correspond to positions of low
probability.
54
n
1
0
1
0
1
0
1
0
0
(a/2)|u(x)|2
(a/2)1/2u(x)
1
1
0
1
0
0.5
x/a
5
0
0.0
0.5
x/a
1.0
Fig. 2.4 The lowest five energy eigenfunctions for the infinite potential well (left )
and the corresponding probability densities (right ). With increasing n, each successive eigenfunction has one more node.
2.7.3
55
Discussion
1. Let us consider an example of system we are dealing with. Suppose an

electron trapped in an atomic-scale potential well of width a = 0.5 nm. The
energy of the ground state is E1 = 2 ~2/2ma2 1.51 eV, the next energy
levels being positioned at 5.02 eV, 13.55 eV, and so on.
2. Classically a particle in an infinite potential well can have zero velocity,
so zero energy. The quantum description shows that the minimum energy
is strictly positive. This is a manifestation of the uncertainty principle since
the particle is localized within x = a/2 so px ~/2x = ~/a and
E=

1 2
1
~2
1
hpx i =
hp2x i hpx i2 =
(px )2
.
2m
2m
2m
2ma2
The actual ground state energy E1 is 2 larger than the lower bound; note
that the dependence on ~, m and a is the same as that of E1 .
The uncertainty principle is often used to provide a quick order of magnitude estimate for the ground state energy.
3. Equation (2.30) gives the probability per unit length of finding the
particle inside the well in the classical description. Let us derive this result
as a limit case of the quantum description. According to the correspondence
principle, classical behaviour is expected for large values of the quantum
number n . We consider an interval of length x inside the well; for large
values of n , the probability density (2.38) has many oscillations on the interval and its average value is
2 D 2 nx E 2 1
1
sin
=
= ,
a
a
a2
a
i.e., the classical result.

4. To make clear why we do not detect the quantum nature of matter at
a macroscopic scale let us consider a mass of 1 kg of energy 1 J trapped in a
potential well of width 1 m. Supposing the system in an energy eigenstate,
Eq. (2.36) gives n 4.3 1033 . The energy spacing to adjacent levels n 1
is
2 ~2
2
|En1 En |
2n = En 4.7 1034 J ,
2ma2
n
much less than the energy of the system and impossibly small to detect;
energy appears to take on a continuous range of values. Further, the probability per unit length has a number of peaks of the order of 1033 . The peak
spacing is 1033 m, and hence unresolvable from each other; the significant
probability density is the averaged one and this coincides with the classical
one.
56
5. Let us choose the axis origin in the middle of the well. Now, the
potential is an even-parity function [V (x) = V (x) for all x]. The energy
eigenfunctions for x [a/2, a/2] reads
r
r
nx n
2
2
n(x + a/2)
un (x) =
sin
=
sin
+
a
a
a
a
2
and by a phase change of in case of need
(p
2/a cos nx/a
un (x) = p
2/a sin nx/a
n odd
n even.
(2.39)
These wavefunctions are alternatively even and odd, so |un (x)|2 = |un (x)|2
for all n and x, that is, the probability density is the same at x and x.
The physical background of this is that there is no reason for the particle to
distinguish between the two sides of a symmetrical well.
The property of energy eigenfunctions to have a definite parity is a general one in case of a symmetric well and useful to simplify the determination
of the TISE solution.
2.8
The rectangular potential barrier. Potential

barrier penetration
We now consider the scattering of a particle by a potential barrier such

as the one shown in Fig. 2.5. This potential barrier can be written mathematically
(
0
x < 0, x > a
V (x) =
(2.40)
V0 0 x a .
The energy of a particle in this potential is E > 0 . We shall consider

the cases 0 < E < V0 and E > V0 separately.
2.8.1
Case 0 < E < V0
Classical mechanics predicts that a particle coming from the left with an
energy 0 < E < V0 is reflected back at x = 0 .
Let us now consider the quantum mechanical treatment. We can immediately write the general solution of the TISE:
C1 exp(ikx) + C2 exp(ikx) x < 0

u(x) = C3 exp(x) + C4 exp(x)
(2.41)
0xa
exp[ik(x a)]
x > a,
57
V (x)
6
V0
Fig. 2.5 A 1-D rectangular potential barrier of width a and height V0 .
A particle is incident from the left.
-x
where
k = (2mE)1/2 /~
(2.42)
= [2m(V0 E))]1/2 /~ .
(2.43)
and
For a particle incident from the left we anticipate that in the region x > a
there is no wave propagating to the left. For simplicity, the amplitude of the
wave in the region x > a has modulus 1 .
By applying the boundary conditions at x = 0 and x = a, we get the set
of algebraic equations
C1 + C2 = C3 + C4 ,
(2.44a)
ik(C1 C2 ) = (C3 C4 ) ,
(2.44b)
C3 exp(a) + C4 exp(a) = 1 ,
[C3 exp(a) C4 exp(a)] = ik .
(2.44c)
(2.44d)
The solution for C1 is

C1 = cosh a + (i/2)(/k k/) sinh a .
(2.45)
There is solution whatever the value of E . It means that the energy

has a continuous spectrum. In other words, the energy of the particle is not
quantized.
Let us consider now the probability flux density. In region x < a there
are two counterpropagating waves: the incident wave and the reflected wave.
The probability current density in this region is (see Problem 2.1)
j(x) =

~k
|C1 |2 |C2 |2 ,
m
x<0
(2.46)
58
while the probability current density in the region x > a is

j(x) =
~k
.
m
(2.47)
We define the transmission coefficient of the barrier as

T =
Here,
|jtransmitted |
.
|jincident |
T =
(2.48)
1
.
|C1 |2
The expression of C1 is introduced here and it yields

!
2m(V0 E)
a .
~2
(2.49)
In order to write the transmission coefficient in a simpler form, we introduce
the dimensionless parameters
r
2mV0
=
a and = E/V0 .
(2.50)
~2
1
T 1 = 1+
4
k
+
k
2
1
V02
sinh2 a = 1+
sinh2
4 E(V0 E)
The parameter characterizes the potential barrier and it will be

strength parameter. The parameter expresses the energy in units
barrier height. The use of these parameters in the expression of the
mission coefficient gives
sinh2 1
T 1 = 1 +
.
4(1 )
called
of the
trans-
(2.51)
The transmission coefficient T is the probability that the particle reaches

the point x = a , thus passing the potential barrier and penetrating into the
region on the right. The phenomenon is called barrier penetration or the
tunnel effect.
Special case: For 1 1 the transmission coefficient is small and

Eq. (2.51) can be approximated:
[(1/2) exp( 1 )]2

exp(2a)
1
T
=
4(1 )
16(1 )
so
T 16(1 ) exp(2a) .
(2.52)
59
1
(a)
0
1
(b)
0
1
(c)
0
1
T
(d)
0
2
E /V0
Fig. 2.6 Transmission coefficient of a rectangular potential barrier versus normalized energy of the incident particle for some values of the barrier parameter : (a)
= 1 , (b) = 2 , (c) = 5 , and (d) = 10 .
2.8.2
Case E > V0
In this case there is no classical forbidden region. The calculations are

performed similarly. Formally, the results can be obtained from the above
analysis by the simple replacement
p
ik = i 2m(E V0 )/~2
This turns sinh x into sin k x and k2 into k2. Exercise:
sin2 1
1
T =1+
.
4( 1)
(2.53)
Figure 2.6 shows the transmission coefficient of a barrier as a function of

the normalized energy for various values of the barrier strength parameter.
2.8.3
Discussion
0 < < 1 . The transmission coefficient is an increasing function of

energy and it can take significant values for sufficiently small values of
60
the strength parameter .

Examples:
1. Electron (me 9.1 1031 kg), V0 = 2 eV, a = 0.1 nm , E =
1 eV . We get 0.72, = 0.5 and T 0.78 ; there is a significant
probability of barrier penetration.
2. Proton (mp 1 836 me ), V0 = 2 eV, a = 0.1 nm , E = 1 eV .
We get 31, = 0.5 and T 3.5 1019 . The probability of

barrier penetration is not significant.
Barrier penetration can also be explained in terms of energytime uncertainty relation. The energy of the particle fluctuates; the magnitude
of the fluctuation is E on a timescale t ~/E . A fluctuation
giving the energy E + E > V0 can enable the particle to pass over
the barrier.
> 1 . The graphs exhibit oscillations and the transmission is unity
for
1 = n , n = 1, 2, 3, . . . .
(2.54)
By introducing the constant of the wave inside the barrier
k = [(2m(E V0 )1/2 /~
(2.55)
the condition for maxima becomes

k a = n .
(2.56)
In other words, the width of the barrier is an integral number of half

wavelengths. This condition was encountered in optics, in the study
of the FabryPerot interferometer. The maxima are explained as a
constructive interference of waves.
2.9
The quantum harmonic oscillator
In classical mechanics, a harmonic oscillator (also known as linear oscillator or simple oscillator) is a physical system that is bound to a position
of stable equilibrium by a restoring force proportional to the displacement
from this position. A typical example of a harmonic oscillator is that of a
mass attached to a spring. The restoring force is the elastic force F given
by Hookes law
F = kx ,
(2.57)
2.9 The quantum harmonic oscillator
61
where x is the displacement and k is the spring constant. The motion of a

body of mass m attached to the spring is governed by Newtons second law
m
d2
x(t) = kx
dt2
(2.58)
whose general solution is

x(t) = A cos(t + ) .
(2.59)
(2.60)
Here,
=
k/m
is the natural oscillating frequency, A is the amplitude of the oscillation,

and is the phase constant; both A and are constants determined by the
initial condition (initial displacement and velocity).
The work of force F between two positions x1 and x2 is
Z x2
1
1
W =
F (x) dx = kx21 kx22
(2.61)
2
2
x1
and this do not depend on the path between them, so a potential energy
V (x) can be defined. As a general rule,
W = V = V (x1 ) V (x2 ) ,
(2.62)
so V (x) = (1/2)kx2 + const; the simple choice V (0) = 0 gives

V (x) = (1/2)kx2 = (1/2)m 2 x2 .
(2.63)
The harmonic oscillator is one of the most important models in mechanics

because any potential V (x) can be approximated as a harmonic potential in
the vicinity of a stable equilibrium point.
We now turn our attention to the quantum description of the harmonic
oscillator. The 1-D TISE with the potential given by Eq. (2.63) is
~2 d2
1
u(x) + m 2 x2 u(x) = E u(x) .
2
2m dx
2
(2.64)
As first step in this equation solving, dimensionless coordinate and energy

are introduced; the substitutions
= (m/~)1/2 x = x
and = E/(~/2)
(2.65)
62
give the equation
d2
u() + ( 2 )u() = 0 .
d 2
(2.66)
There is not a straightforward method to solve this equation. We first investigate the asymptotic behavior of u(y). For large values of ||, the parameter
is negligible compared to 2 and the above equation becomes
d2
u() 2 u() = 0 .
d 2
The approximate solutions of this equation are
u() = C exp( 2/2) ,
Indeed,
C = const .
d2
u() = ( 2 1)u() 2 u() for large || .
d 2
The function defined by u() = exp( 2/2) is not satisfactory because it becomes infinite as || and the function defined by u() = exp( 2/2)
approaches 0 at infinity, so it is well-behaved. Retaining the asymptotic
behavior given by exp( 2/2) , we are led for searching solutions of the form
u() = H() exp( 2/2) ,
(2.67)
where H() is a function to be determined.

Substitution of Eq. (2.67) into Eq. (2.66) gives
d2
d
H() 2 H() + ( 1)H() = 0 .
2
d
d
(2.68)
The solution of this differential equation is searched in the form of a series

H() = a0 + a1 + a2 2 + .
(2.69)
This form of H is inserted into Eq. (2.68); the coefficient of s (s N) in

left-hand side of the equation is
(s + 1)(s + 2)as+2 2sas + ( 1)as
and it must be zero, so
as+2 =
2s + 1
as ,
(s + 1)(s + 2)
s N.
(2.70)

E/~
63
..
.
4
4
3
3
2
Fig. 2.7 Energy level diagram for the quantum

harmonic oscillator.
2
1
1
Ground state
In the limit of large s , as+2 /as = 2/s , and this ratio can also be encountered
in the Taylor expansion of exp( 2 ):
2
e = c0 + c1 + c2 2 + c3 3 + = 1 + 2 +
4 6
+
+ .
2!
3!
Indeed, the ratio of adjacent coefficients for large s is

1
2
c2s+2
1
=
.
=
c2s
s+1
s
2s
It follows that H() and exp( 2 ) have the same asymptotic behaviour. Coming back to the solution (2.67) of Schr
odinger equation, this behaves like
exp( 2/2) for large . This function diverges and is not an acceptable solution. The only way to avoid the divergence of the wave function is to terminate the series (2.69) after a finite number of terms. Examining Eq. (2.70)
we find that an (n N) is the last term in the series if 2n + 1 = 0 , which
means
= 2n + 1 n , n N .
By use of Eq. (2.65), the possible values of the energy are given by
En = (~/2)n = ~(n + 1/2) ,
n N.
(2.71)
The energy of the quantum oscillator is thus quantified. The energy levels
are equally spaced and the minimum energy is ~/2 > 0 (see Fig 2.7). The
positive value of the ground state energy is consistent with the uncertainty
principle, since zero energy would require x = 0 and px = 0, simultaneously.
64
Table 2.1 First six Hermite polynomials.

n
0
1
2
3
4
5
Hn (x)
1
2x
4x2
8x3 12x
16x4 48x2 + 12
32x5 160x3 + 120x
We now focus on the energy eigenfunctions determination. The use of

n into Eq. (2.68) gives
d2
d
H() 2 H() + 2nH() = 0 .
2
d
d
(2.72)
The solution of this equation is known as Hermite polynomial of order n and

is usually expressed in the form
Hn () = (1)n e
dn 2
e .
d n
(2.73)
Table 2.1 lists first few Hermite polynomials.

The solution of Schr
odinger equation for the energy En reads now
un (x) = Nn exp(2 x2/2) Hn (x) ,
where Nn is the normalization constant. By imposing
Z
|un (x)|2 dx = 1 ,
(2.74)
(2.75)
it is found
Nn =
2n n!
(2.76)
Figure 2.8 shows first few energy eigenfunctions and corresponding probability per unit length.
Applications of the quantum oscillator
Study of the oscillations of the atoms of a molecule about their equilibrium position
Study of the oscillations of atoms of a crystalline lattice
65
n
0.5
0.0
0.5
0.5
0.0
0.5
0.5
0.0
0.5
0.5
0.0
|n(x)|
n(x)
0.5
4
0.0
1/2
0.5
0.5
0
x
0.3
0.2
0.1
0.0
0.3
0.2
0.1
0.0
0.3
0.2
0.1
0.0
0.3
0.2
0.1
0.0
0.3
0.2
0.1
0.0
4
5
2
0
x
Fig. 2.8 The lowest five energy eigenfunctions for the quantum harmonic oscillator
(left ) and the corresponding probability densities (right ).
Table 2.2 Vibrational frequency of some diatomic molecules.

Molecule
C2
N2
O2
NO
CO
/(1013 Hz)
4.921
7.074
4.374
5.708
6.508
66
Study of a the electromagnetic field of radiation

One mode of the radiation field is treated as a quantum oscillator. For
a radiation field of angular frequency , the energy level separation is
~. Suppose the radiation field in the energy eigenstate n; the energy
of the field is n~ above the ground state. One can associate a set of n
identical particles to the radiation field, each one carrying the energy
~; these particles are called photons. The transition of the radiation
field from one energy eigenstate to another corresponds to the creation
(emission) or destruction (absorption) of a number of photons.
The interaction between the radiation field and an atom can produce
jumps of the atom from one state to another. This subject was treated
phenomenologically in Sect. 1.8. The quantum theory confirms Einsteins theory. If the field is in an excited state (n 1), the interaction
processes are the stimulated (induced) emission and absorption. If the
radiation field is in its ground state1 and the atom in an excited state,
the fluctuations of the field induce the dezexcitation of the atom; the
phenomenon is the spontaneous emission.
2.10
Three-dimensional Schr
odinger equation
Unlike the 1-D case, 3-D TISE [Eq. (2.24)] is a partial differential equation which gives rise to considerable mathematical complications in general;
solving of the 3-D TISE will be limited below to those cases where the separation of variables technique can be used.
Let us consider the case where the potential energy V (r) can be written
as a sum of three terms, each of which is a function of only one of the three
Cartesian coordinates:
V (r) = Vx (x) + Vy (y) + Vz (z) .
(2.77)
We look for wavefunctions that express as a product of three one-dimensional

functions,
u(r) = X(x) Y (y) Z(z) .
(2.78)
Substituting Eqs. (2.77) and (2.78) into Eq. (2.24), dividing by X(x)Y(y)Z(z)
1
Classically, there is no radiation field.
2.10 Three-dimensional Schr

odinger equation
67
and rearranging, we get

~2
~2 1 d2 Y (y)
1 d2 X(x)
+ Vx (x) +
+ Vy (y)
2m X(x) dx2
2m Y (y) dy 2

~2 1 d2 Z(z)
+ Vz (z) = E . (2.79)
+
2m Z(z) dz 2
This equation says that a function of x alone (the term inside the first
square bracket), plus one of y alone, plus one of z alone, equals a constant
E. The equation can only be true if each square bracket is independently
constant. Denoting Ex , Ey , and Ez the constants, Eq. (2.79) split into three
one-dimensional TISEs:
~2 d2 X(x)
+ Vx (x)X(x) = Ex X(x) ,
(2.80a)
2m dx2
~2 d2 Y (y)
+ Vy (y)Y (y) = Ey Y (y) ,
(2.80b)
2m dy 2
~2 d2 Z(z)
+ Vz (z)Z(z) = Ez Z(z) .
(2.80c)
2m dz 2
After solving these three problems, the energy eigenfunctions of the 3-D
TISE [Eq. (2.24)] are given by Eq. (2.78) and the energy eigenvalues are
given by
(2.81)
E = Ex + Ey + Ez .
2.10.1
Example: The three-dimensional infinite well
As an example of a 3-D TISE solving we consider a particle of mass m

trapped in a 3-D infinitely deep potential well of sides ax , ay and az :
(
0
0 x ax , 0 y ay , 0 z az
V (x) =
(2.82)
otherwise.
This potential approximates, for example, that of the electrons in a metal.
Based on the results of Sect. 2.7, an energy eigenstate is specified by three
quantum numbers, nx , ny , nz = 1, 2, . . . . The state specified by (nx , ny , nz )
has the energy eigenfunction inside the well given by
s
8
nx
ny
nz
unx ny nz (x, y, z) =
sin
sin
sin
(2.83)
ax ay az
ax
ay
az
and the energy of the state is
Enx ny nz
2 ~2
=
2m
n2x n2x n2x

+ 2 + 2
a2x
ax
ax
68
Table 2.3 First few energy eigenvalues and corresponding degeneracies of the
particle of mass m in the 3-D infinite potential well with all side lengths equal to a.
nx , ny , nz
1, 1, 1
1, 1, 2
1, 2, 2
1, 1, 3
2, 2, 2
1, 2, 3
Enx ny nz /( 2 ~2/2ma2 )
3
6
9
11
12
14
Degeneracy
single
three-fold
three-fold
three-fold
single
six-fold
Degeneracy
It is possible that distinct quantum states have the same energy value:
Enx ny nz = Enx ny nz
for
(nx , ny , nz ) 6= (nx , ny , nz ) .
Such an energy level is said to be degenerate; the degeneracy of that level is

equal to the number of distinct quantum states that have the same energy
eigenvalue.
To exemplify, let us assume that the potential well considered above has
all side lengths equal, ax = ay = az = a . The expression of the energy levels
becomes

2 ~2
Enx ny nz =
n2x + n2y + n2z .
(2.84)
2
2ma
The distinct states (nx , ny , nz ) and (nx , ny , nz ) that satisfy the condition
2
2
n2x + n2y + n2z = n2
x + ny + nz
are degenerate.
The minimum energy is obtained for (nx , ny , nz ) = (1, 1, 1) and there is
not another way to get the same energy; the ground level is therefore not
degenerate. The first excited level is obtained for (nx , ny , nz ) = (1, 1, 2),
(1, 2, 1), or (2, 1, 1); the energy level is three-fold degenerate. Table 2.3
describes the lowest few energy levels. The degeneracy in all the cases included in the table are related to a symmetry in the physical system; such
degeneracies are called systematic degeneracies. Degeneracies may also occur not related to a symmetry; for example, (nx , ny , nz ) = (3, 3, 3) and
(nx , ny , nz ) = (1, 1, 5) give the same energy (32 + 32 + 32 = 12 + 12 + 52 ).
Such a degeneracy is referred to as accidental degeneracy.
2.11 Problems
2.11
69
Problems
2.1 A particle of mass m and energy E is placed in a region of the Ox axis

where V (x) = V0 = const . Calculate the probability current density of the
particle for
(a) E > V0 .
(b) E < V0 .
Interpret the results.
Solution. The solution of the 1-D TDSE in the region V (x) = V0 = const is
(x, t) = u(x) exp[i(E/~)t] ,
where
(a)
p u(x) = A exp(ikx) + B exp(ikx) ; A and B are complex constants and
k = 2m(E V0 )/~ .
(b)
p u(x) = A exp(x) + B exp(x) ; A and B are complex constants and
= 2m(V0 E)/~ .
We make use of Eq. (2.20); for the stationary state here, the probability current
density acquires the form

~
d
d
j(x) = i
u(x) u (x) u (x) u(x) .
2m
dx
dx
(a) We get

~k
|A|2 |B|2 .
m
The (total) probability current density expresses as a difference of two currents:
j(x) =
j(x) = j+ (x) j (x) ,

where j+ (x) = (~k/m)|A|2 is a probability current density in the positive Ox direction and j (x) = (~k/m)|B|2 is a probability current density in the negative Ox
direction.
(b) We get
j(x) = i
~
~
2~
(AB + A B) = i (2i)Im(AB ) =
Im(AB ) .
m
m
m
A necessary condition for a non-zero probability current is that both A and B are
non-zero.
2.2 Determine the ground state energy of an electron confined to an infinite

square well of width equal to the diameter of a hydrogen atom, a = 0.11 nm.
Solution. Equation (2.36) is used. By use of ~, me and e from Appendix A,
E1 33.6 eV.
70
2.3 A particle in an infinite square well is described by the initial wavefunction

(
N x(a x) 0 x a
(x) =
0
otherwise,
where N is a complex constant.
(a) Normalize the wavefunction.
(b) Determine the probabilities of the energy eigenstates.
Solution. (a)
Z
|(x)|2 dx = |N |2
x2 (a x)2 dx = |N |2
(a2 x2 2ax3 + x4 ) dx
r

1 5
1 5 1 5 1 5
30
2
2
a a + a =
a |N |
|N | =
.
= |N |
3
2
5
30
a5
p
As arg N has no physical meaning, we choose N = |N | = 30/a5 .
(b) We write as a linear combination of the energy eigenfunctions given by
Eq. (2.37):
X
(x) =
cn un (x) .
1=
n=1
The coefficient cn is

r r Z a
8 15
2 30
nx
n odd
cn =
un (x) (x) dx =
x(a
x)
sin
dx
=
3 n3
5
a
a
a
0
0
n even.
Z
The probability pn of the energy eigenstate un is
960
n odd
pn = |cn |2 = 6 n6
0
n even.
The probability of the state u1 is p1 = 960/ 6 0.9986 very close to one indicating
that the first state dominates.
2.4 Consider a particle of mass m in a 1-D potential well V (x).

(a) Prove that there is no degeneracy in a bound state.
(b) Prove that the energy eigenfunction of a bound state can always be
chosen real in the coordinate basis.
Solution. (a) Let u1 and u2 be two solutions of Eq. (2.27) for the same energy E:
~2 d2
u1 (x) + V (x) u1 (x) = E u1 (x)
2m dx2
2.11 Problems
71
and
~2 d2
u2 (x) + V (x) u2 (x) = E u2 (x) .
2m dx2
We multiply the first equation by u2 and the second equation by u1 , then substract
the equations. We get
u1
or
d2
d2
u2 (x) u2 2 u1 (x) = 0 ,
2
dx
dx
d
dx

du2 (x)
du1 (x)
u1
u2
=0
dx
dx
so that
du2 (x)
du1 (x)
u2
= const .
dx
dx
To determine the constant, we consider x or x where u1 and u2 vanish.
It follows that
du2 (x)
du1 (x)
u1
u2
= 0,
dx
dx
or
du2
du1
=
.
u2
u1
u1
The integration gives u2 = const u1 , i.e., the two energy eigenfunctions are linearly
dependent.
(b) Let u be solution of Eq. (2.27) for the energy E:
~2 d2
u(x) + V (x) u(x) = E u(x) .
2m dx2
We write the energy eigenfunction in the form

u(x) = Re u(x) + i Im u(x) .
The use of this form into the above equation reveals that both the real and the imaginary parts of u satisfy TISE with eigenvalue E. As there is just one independent
solution, the energy eigenfunction can be chosen Re u(x) [or Im u(x)].
72
Appendix A
Fundamental physical
constants
The tables give values of some basic physical constants recommended by
the Committee on Data for Science and Technology (CODATA) based on
the 2006 adjustment [11, 12]. The standard uncertainty in the last two digits
is given in parenthesis.
74
Table A.1 An abbreviated list of the CODATA recommended values of the fundamental constants of physics and chemistry.
Quantity
speed of light in vacuum
magnetic constant
electric constant 1/0 c2
Newtonian constant of gravitation
Avogadro constant
molar gas constant
Boltzmann constant R/NA
Symbol
c, c0
0
0
G
NA
R
k
molar volume of ideal gas

(T = 273.15 K, p = 101.325 kPa)
Loschmidt constant NA /Vm
elementary charge
Faraday constant NA e
Planck constant
Value
299 792 458 m s1 (exact)
4 107 N A2
8.854 187 817... 1012 F m1
6.674 28(67) 1011 m3 kg1 s2
6.022 141 79(30) 1023 mol1
8.314 472(15) J mol1 K1
1.380 6504(24) 1023 J K1
8.617 343(15) 105 eV K1
Vm
n0
e
F
h
22.413 996(39) 103 m3 mol1

2.686 7774(47) 1025 m3
1.602 176 487(40) 1019 C
96 485.3399(24) C mol1
6.626 068 96(33) 1034 J s
4.135 667 33(10) 1015 eV s
1.054 571 628(53) 1034 J s
6.582 118 99(16) 1016 eV s
9.109 382 15(45) 1031 kg
0.510 998 910(13) MeV
1.758 820 150(44) 1011 C kg1
1.672 621 637(83) 1027 kg
1.007 276 466 77(10) u
938.272 013(23) MeV
1.674 927 211(84) 1027 kg
1.008 664 915 97(43) u
939.565 346(23) MeV
1836.152 672 47(80)
7.297 352 5376(50) 103
137.035 999 679(94)
10 973 731.568 527(73) m1
13.605 691 93(34) eV
h/2
electron mass
energy equivalent in MeV
electron charge to mass quotient
proton mass
mp = Ar (p) u
neutron mass
mn = Ar (n) u
proton-electron mass ratio
fine-structure constant e2/40 ~c
inverse fine-structure constant
Rydberg constant 2 me c/2h
R hc in eV
Wien displacement law constants
b = max T
b = max /T
StefanBoltzmann constant
( 2/60)k 4/~3 c2
Bohr radius /4R = 40 ~2/me e2
Compton wavelength h/me c
classical electron radius 2 a0
Bohr magneton e~/2me
nuclear magneton e~/2mp
~
me
me c2
e/me
mp
mp c2
mn
mn c2
mp /me
1/
R
b
b
2.897 7685(51) 103 m K

5.878 933(10) 1010 Hz K1
a0
C
re
B
5.670 400(40) 108 W m2 K4

0.529 177 208 59(36) 1010 m
2.426 310 2175(33) 1012 m
2.817 940 2894(58) 1015 m
927.400 915(23) 1026 J T1
5.788 381 7555(79) 105 eV T1
5.050 783 24(13) 1027 J T1
3.152 451 2326(45) 108 eV T1
75
Table A.2 The values in SI units of some non-SI units.

Name of unit
Symbol Value in SI units
angstrom
A
0.1 nm = 100 pm = 1010 m
a
electron volt : (e/C) J
eV
1.602 176 487(40) 1019 J
b
(unified) atomic mass unit 1 u = mu
= (1/12)m(12 C) = 103 kg mol1/NA u
1.660 538 782(83) 1027 kg
a
The electronvolt is the kinetic energy acquired by an electron in passing through
a potential difference of one volt in vacuum.
b
The unified atomic mass unit is equal to 1/12 times the mass of a free carbon 12
atom, at rest and in its ground state.
76
78
B Greek letters used in mathematics, science, and engineering
Appendix B
Greek letters used in

mathematics, science, and
engineering
Name of letter
alpha
beta
gamma
delta
epsilon
zeta
eta
theta
iota
kappa
lambda
mu
nu
xi
omicron
pi
rho
sigma
tau
upsilon
phi
chi
psi
omega
Capital letter
A
B
E
Z
H
I
K
M
N
Lower-case letter
o
,
,
,
Bibliography
[1] H. Haken and H. C. Wolf, The Physics of Atoms and Quanta (7th edition),
Springer-Verlag, Berlin (2005).
[2] R. Eisberg and R. Resnick, Quantum Physics of Atoms, Molecules, Solids,
Nuclei, and Particles (2nd edition), John Wiley & Sons, New York (1985).
[3] Serway
[4] I. M. Popescu, Fizic
a, Vol. II, Editura Didactica si Pedagogica Bucuresti, Bucuresti (1983).
[5] V. Florescu, Lectii de Mecanic
a Cuantic
a, Editura Universitatii din Bucuresti,
Bucuresti (2007).
[6] C. Cohen-Tannoudji, B. Diu, and F. Laloe, Quantum Mechanics, Vols. I and
II, John Wiley & Sons, New York (1977).
[7] D. J. Griffiths, Introduction to Quantum Mechanics, Prentice Hall (1995).
[8] B. H. Bransden and C. J. Joachain, Quantum Mechanics (2nd edition), Pearson, London (2000).
[9] R. Shankar, Principles of Quantum Mechanics (2nd edition), Kluwer Academic, New York (1994).
[10] Properties of solids, in CRC Handbook of Chemistry and Physics, Internet
Version 2005, David R. Lide, ed., http://www.hbcpnetbase.com, CRC Press,
Boca Raton, FL (2005).
[11] P. J. Mohr, B. N. Taylor, and D. B. Newell, CODATA recommended values
of the fundamental physical constants: 2006, Rev. Mod. Phys 80(2), 633730
(2008); J. Phys. Chem. Ref. Data 37(3), 11871284 (2008). The article can also
be found at http://physics.nist.gov/cuu/Constants/papers.html.
[12] CODATA Internationally recommended values of the fundamental physical
constants, http://physics.nist.gov/cuu/Constants.

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ELEMENTS

2 Postulates of quantum mechanics and applications

2.7.2 Energy eigenvalues and eigenfunctions . . . . . . . . .

B Greek letters used in mathematics, science, and engineering 77

exponential function, ez = exp(z)

1 The experimental foundations of quantum mechanics

It is well known that every body with non-zero absolute temperature

1.1 Thermal radiation

Fig. 1.1 A cavity with a small hole behaves as

This result is known as Kirchhoff s radiation law (1859). According to

1 The experimental foundations of quantum mechanics

A grey body is defined as a body with constant emittance/absorptance

Quantitative laws for blackbody radiation

where 5.67 108 W m2 K4 is StefanBoltzmann constant. The law

1.1 Thermal radiation

where c is the speed of light in vacuum.

known as RayleighJeans formula. The comparison with the experimental

1 The experimental foundations of quantum mechanics

Plancks radiation law

To express the radiant exitance E , Eq. (1.5) is used:

The photoelectric effect consists in the ejection of electrons from a solid

1.2 Photoelectric effect

Fig. 1.2 Spectral energy density (, T ) of a blackbody at a few temperatures.

The phenomenon was first observed by Heinrich Hertz in 1887; he noticed

1 The experimental foundations of quantum mechanics

A typical arrangement for the study of the photoelectric effect is depicted

1.2 Photoelectric effect

frequency, 0 in Fig. 1.5, is called threshold frequency. It is experimentally

1 The experimental foundations of quantum mechanics

The stopping voltage as a function of the radiation frequency is a straight line

1.3 Waveparticle duality of radiation

Waveparticle duality of radiation

The phenomena of the interference and diffraction can be explained only

It is natural to extend this formula for the quantum of radiation, i.e.,

1 The experimental foundations of quantum mechanics

wave is = k/c and the photon momentum can be written

This formula can be written with vectors,

To sum up, the two behaviours of radiation are linked by PlanckEinstein

The existence of photons is also demonstrated by experiments in which

The constant C 2.426 1012 m is nowadays called Compton wavelength

1.4 Compton effect

Fig. 1.6 In Compton scattering an x-ray

as required by the conservation of energy of momentum. Here, T and pe are

After performing the elementary calculations it is obtained Eq. (1.21), where

1 The experimental foundations of quantum mechanics

By the early 1900s, the following observations concerning the atomic

where C 364.6 nm . This formula was written by Johannes Rydberg (1888)

1.6 Bohr model of the hydrogen atom

Bohr model of the hydrogen atom

1 The experimental foundations of quantum mechanics

For every atom there is an infinite number of stationary states in which

We are now in a position to solve the problem. Newtons second law

Combining Eqs. (1.31) and (1.32), we find

1.6 Bohr model of the hydrogen atom

The energy of the atom in state n is

Let us now calculate the frequencies of the hydrogen spectrum. In the

The wavelength n1 n2 = c/n1 n2 of the radiation is given by

1 The experimental foundations of quantum mechanics