Quantum Mechanics I

College of Natural and Computational Science

Department of Physics

Lecture note for (Phys-3402)

By
Yimenu Yeshiwas

Debark, Ethiopia
March, 2015
 Contents

1. Origin and Development of Quantum Mechanics . . . . . . . . . . . . . . . . 4

1.1 Limitation of Classical Physics . . . . . . . . . . . . . . . . . . . . . . . 4

1.2 Review of modern physics . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1.2.1 1.2.1. Black body radiation . . . . . . . . . . . . . . . . . . . . . 5

1.2.2 1.2.2. Quantum theory of light . . . . . . . . . . . . . . . . . . . 5

1.2.3 1.2.3. Photoelectric Effect . . . . . . . . . . . . . . . . . . . . . . 6

1.2.4 1.2.4. Compton Effect . . . . . . . . . . . . . . . . . . . . . . . . 6

1.2.5 1.2.5. Matter waves . . . . . . . . . . . . . . . . . . . . . . . . . . 7

1.2.6 1.2.6. Bohr atomic model and atomic spectra . . . . . . . . . . 7

1.3 1.3. Development of quantum mechanics . . . . . . . . . . . . . . . . 11

1.4 1.3. Uniqueness and role of quantum physics . . . . . . . . . . . . . . 11

2. Mathematical development of quantum mechanics . . . . . . . . . . . . . . 14

2.1 Measurments and observables . . . . . . . . . . . . . . . . . . . . . . . 14

2.2 Uncertainty principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2.2.1 Wave packet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

2.3 The Concept of State . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

2.4 Superposition Principle . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

Contents Contents

2.5 Wave functions and physical interpretation . . . . . . . . . . . . . . . . 20

2.6 Expectation value of dynamical variables . . . . . . . . . . . . . . . . . 20

2.7 Probability density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

3. Operator Algebra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

3.1 Vector Space and Hilbert Space . . . . . . . . . . . . . . . . . . . . . . . 24

3.1.1 Linear Vector Space . . . . . . . . . . . . . . . . . . . . . . . . . . 24

3.1.2 Hilbert Space . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

3.1.3 Dirac Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

3.1.4 Superposition Principle . . . . . . . . . . . . . . . . . . . . . . . 26

3.1.5 Eigenvalue and Eigenfunctions . . . . . . . . . . . . . . . . . . . 26

3.2 Adjoint and Hermitian operator . . . . . . . . . . . . . . . . . . . . . . . 26

3.3 Fundamental postulates of quantum mechanics . . . . . . . . . . . . . 27

4. Schrodinger and Heiseberg Equation . . . . . . . . . . . . . . . . . . . . . . 29

4.1 solution of schrodinger equation . . . . . . . . . . . . . . . . . . . . . . 30

4.2 schrodinger . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

4.3 Heisenberg picture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

5. The harmonic oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

5.1 Correspondence principle . . . . . . . . . . . . . . . . . . . . . . . . . . 32

5.2 Time evolution operators . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

5.3 Question to practice for exit exam competence . . . . . . . . . . . . . . 33

3
 1

Origin and Development of Quantum Mechanics

1.1 Limitation of Classical Physics

Classical mechanics explains well our daily experience and macroscopic systems. But
for particles at high speed, it fail to fit with research results. For atomic and sub-
atomic particles including elementary particles explanations and theories of classi-
cal physics show a clear deviation from experimental findings. Classical mechanics
fail to explain Photoelectric effect, Quantization of energy, Space-time concepts, Rel-
ativity in length, time, velocity, momentum and energy, Wave particle duality and
Probabilistic nature of measurments.

As the result, the branch of classical physics like mechanics, acoustics, thermo-
dynamics, electricity and optics had to be elarged. This is because of the increase of
knowledge on the structure of matter, atoms and quanta. So classical physics is com-
pemented by atomic physics and quantum mechanics (the physics of light or energy
quanta).
1.2 Review of modern physics Origin and Development of Quantum Mechanics

1.2 Review of modern physics

1.2.1 1.2.1. Black body radiation

Black body is a body that absorbs all radiations incident on it regardless of frequency.
If a black body s heated to a temprature T, it would emit radiation of all frequencies.
This is called black body radiation. In 1900; Max Plank removed the discrepancies be-
tween expriments and theory by proposing an emperical formula. He assumed that
the atoms of the walls of black body behave like tiny electromagnetic oscillators, each
having characteristic frequency of vibration. Also an oscillator of a given frequency
emits and absorbs electromagnetic radiation of the same frequency. The oscillators
emit or absorb energy in a bundle or packet (quanta)of size given by

E = hν (1.1)

(this is the first idea of quantization)where h = 6.62 × 10−34 J/s is Plank’s constant and
ν is frequency of radiation.

1.2.2 1.2.2. Quantum theory of light

Light is nothing but an electromagnetic wave or radiation produced by the interac-

tion of the electric and magnetic fields of the sun. Electromagnetic waves have a dual
nature as a wave they can be refelected, diffracted, refracted and polarized and as a
particle they consist of stream of particle (like photons). Photons are particles with
no mass dimension but with momentum (p = ~k) and energy (E = pc). Spectrum of
electromagnetic waves consists of x-rays, gamma rays, ultraviolet light, white light,
infrared light radio wave...

Note The more the intensity, the more visible is the wave. The smaller the wave
length, the higher the frequency and the more energetic is the wave.

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1.2 Review of modern physics Origin and Development of Quantum Mechanics

1.2.3 1.2.3. Photoelectric Effect

Elecromagnetic waves incident on a metal surface produce electrons. This electrons

are called photoelectrons. The phenomenons is photoelectric effect. In other words,
Photoelectric effect is the process of emission of electrons from metal surface by the
action of light. As the electrons are weekly bounded to the metal surface, light in-
cident on a metal give the electrons enough extra kinetic energy to allow them to
escape. The minimum extra kinetic energy that allows the electrons to escape from a
metal is called Work function (w0 ). It is the minimum binding energy of the electron
to the material. w0 = h0 where w0 is the critical (threshold frequency) below which no
photoelectrons is produced. The movement of photoelectrons produces photocur-
rent I. Einstein’s Theory From the Max-Plank idea of quantization, Einstein proposed
that light is not only emitted at a time in certain quanta, but also propagate as indi-
vidual quanta of light photons. According to him, each photon has energy of E = hν.
The energy of the incident radiation is transferred to the electron while it is inside the
material.

K = hν − hν0 (1.2)

Kmax = eV0

Where V0 is the retarding potential

2
Kvmax
= hν − hν0 = eV0 (1.3)
2

1.2.4 1.2.4. Compton Effect

The quantum theory of light postulates that photons behaves as particles except the
absence of rest mass. The concept of particle nature of light (photon) was further
verified by Arther. H. Compton in 1923. He measured the scattering of x-ray photons
by the electrons at rest (not bound). The explanation of this experiment in the wave
picture of light. But, this can be done by assuming that photons behave like parti-

6
1.2 Review of modern physics Origin and Development of Quantum Mechanics

cles giving off part of their energy and momentum to the electron up on collision.
The photon losses energy 4 by the time which is equal to the energy gained by the
electron.

The photoelectric and compton effects can only be understood by assuming that
light (radiation) consists of individual particles called photons with momentum p.

1.2.5 1.2.5. Matter waves

The first bold step (radical ideal with no experimental confirmation ) towards to new
mechanics of atomic systems was taken by de Broglie (an outstanding French experi-
mental physicist) in 1923. He postulated that as photons have wave and particle dual
nature, perhaps all forms of matter have wave as well as particle properties. A moving
body behaves in certian ways as though it has a wave nature and the waves associ-
ated to particles are called matter waves. De Broglie used Einstein’s special theory of
relativity together with Plank’s quantum theory of light to establish the wave proper-
hν
ties of particles. Accordingly, E = hν = pc is the energy and p = c
is the momentum
of a photon. But c = λν; p = hν/λν; p = h/λ, λ = h/p; is the wavelength of a photon
expressed in terms of its momentum. De Broglie assumed that this should also apply
for particles. The momentum of a particle of mass m moving at a speed v is

p = mv (1.4)

h
Its de Broglie wavelength is λ = h/p = mv
; is de Broglie wavelength of particles.

1.2.6 1.2.6. Bohr atomic model and atomic spectra

Bohr model of an atom The first theory of the atom to meet with any success was put
forward by Niels Bohr in 1913. The concept of matter waves leads in a natural way to
this theory. Niels Bohr accepted the atomic spectra completely and got an equation
based on the following assumptions.

1. Electrons move in a circular orbit around the nucleus in accordance with the
coulomb law of electrostatic force.

2. Of the infinite number of orbital states that are possible, according to classi-

7
1.2 Review of modern physics Origin and Development of Quantum Mechanics

cal theory, only those states are allowed for which the atomic system posses certain
discrete energies. These states are called stationary states.

3. An atom can interact with radiation only by making a sudden and discontinu-
ous transition from one of the stationary states to an other by emitting or absorbing
an electromagnetic photon (energy quantum) whose energy is exactly equal to the
difference in energy between the two states. E = Ei − Ef = hν is loss or emission
0 0
E = Ef − Ei = hν is absorbed where Ei is the energy of the upper stationary state
and Ef is the energy of the lower stationary state

4. There exist a state of energy for the atom called ground state or stable(normal)state
from which no further photon emission is allowed even though in this state charges
are under going accelerated motion.

5. The angular momentum of the system in a stationary state is an integral mul-

tiple of ~, where ~ = h/2π, Ln = n~, n = 1, 2, 3,..... -quantization of angular mo-
nλ
mentum.but L = mvr, nλ = mvr, v = mr
is the orbital velocity of electron which is
e nλ e 4πε0 ~2 2
v= √
4πε0 mr
and n is the principal quantum number. mr
= √
4πε0 mr
, rn = me2
n

r n = a0 n 2 (1.5)

4πε0 ~2 4πε0 ~2
Where, a0 = me2
is called the Bohr radius, a0 = me2
= 0.533A0 for electron and n =
1. This shows that the orbital radius is quantized. The smallest diameter of hydrogen
atom is so 2a0 = 1A0 .

Energy levels

The total energy of the electron in hydrogen atom in the planetary model of the
atom is given by
e2
E=− (1.6)
4πε0 r

e2
En = − (1.7)
4πε0 rn
4πε0 ~2 2
but rn = me2
n
e4
En = − (1.8)
32πε20 ~2 n2

8
1.2 Review of modern physics Origin and Development of Quantum Mechanics

−13.6eV
En = − (1.9)
n2
where n = 1, 2, 3, ..... is the principal quantum number. From this equation we see
that the energy is quantized ( descrete) and depends only on the principal quantum
number E1 = 13.6eV is the ground energy or ground level(state), n = 2, 3, 4,.... are
called exited levels(states).

Atomic spectra

Emision of a quanta of light (photon) occur when the atom in an excited state
with a principal quantum number n = ni decays to any lower state with a principal
quantum number n = nf or make a transition from upper excited states to any lower
excited. From the third Bohr assumption E = Ei − Ef = hν is the quanta of energy
emitted with frequency ν. But ν = c/λ and Eni = − −13.6eV
n2 i

c
h = Ei − Ef (1.10)
λ

1 Ei − Ef
= (1.11)
λ hc

1 − −13.6eV
n2i
+ 13.6eV
n2f
= (1.12)
λ hc

1 13.6eV 1 1
= ( 2 − 2) (1.13)
λ hc nf ni

1 1 1
= R∞ ( 2 − 2 ), (1.14)
λ nf ni
R∞ = 1.097×107 m−1 is called Rydberg constant which has a meaning that the mass of
the nucleus is infinite as compared to the mass of the electron. This expression shows
that the emitted quanta of light in the spectrum will have a specific or descartes wave-
length (quantization of wave length).

1 1 12
Lymanseriesnf = 1, = R∞ ( 2 − ), ni = 2, 3, 4, ....... (1.15)
λ 1 ni

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1.3 1.3. Development of quantum Origin and Development of Quantum Mechanics
mechanics

1 1 12
Balmerseriesnf = 2, = R∞ ( 2 − ), ni = 3, 4, 5, ....... (1.16)
λ 2 ni

1 1 12
P aschenseriesnf = 3, = R∞ ( 2 − ), ni = 4, 5, 6, ....... (1.17)
λ 3 ni

1 1 12
Brackettseriesnf = 4, = R∞ ( 2 − ), ni = 5, 6, 7, ....... (1.18)
λ 4 ni

1 1 12
P f undseriesnf = 5, = R∞ ( 2 − ), ni = 6, 7, 8, ....... (1.19)
λ 5 ni
The spectral series produced is summarized as follows Notice that the energy of the
level

Schematic diagram

is called binding energy and atomic spectra is produced when atoms move from
any upper level to any lower level. But atoms need extra energy to move from any of
the lower states to any upper level called excitation. This energy is termed as excita-
tion energy which is equal to the energy difference or gap between the two levels. The
state with n = ∞ corresponds to a state in which the electron is completely removed
from the atom or the atom is called ionized where as the energy is called ionization
energy.

Limitations of Bohr model

Xcircular orbits allowed are arbitrary.

Xcannot be generalized to atomic systems having two or more electrons.

Xquantization of angular momentum is introduced in Adhoe way

Xthe stability problem is bypassed.

Due to these limitations it is called Old quantum theory

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1.3 1.3. Development of quantum Origin and Development of Quantum Mechanics
mechanics

1.3 1.3. Development of quantum mechanics

Quantum theory is branch of physics that,which is emerged in 20th century, attempts
to describe the behavior of matter and radiation at the atomic level and it had enor-
mous impact on almost all areas of science including Biology, Chemistry and Cos-
mology. By the end of 19th century, most observable phenomena were explained by
Newton’s laws of motion (from billard balls to planets) and Maxwell equations (elec-
tric, magnetism and light). During this time exhaustive studies to measure the radi-
ation of energy from hot bodies in a cavity (black body) showed that the measured
value of radiation energy from a hot body in a cavity could not be accurately pre-
dicted using classical mechanics. Nobody was able to describe the low temperature
specific heat of solids and the appearance of only five degree of freedom in the mo-
tion of diatomic molecules at ordinary temperature. Quantum mechanics is started
by Max Plank (German professor) who presented a paper to explain the black body
spectrum in terms of the assumed emission and absorbtion of electromagnetic ra-
diation in a discrete quanta (bundle) of energy E. The quanta of energy absorbed or
emitted is frequency of radiation ν times the universal constant h(Plank’s constant)
as. E = nhν; Which is the first idea of quantization.

Table 1.1: Classical Mechanics versus Quantum Mechanics

No Classical Mechanics Quantum Mechanics

1 physical quantities are continuous physical quantities are discrete
2 physical quantities are diterministic physical quantities are probabilistic
3 deals with macroscopic systems deals with microscopic systems at atomic level

1.4 1.3. Uniqueness and role of quantum physics

There are several features of quantum mechanics that make it different from classical
mechanics. This includes

1. Particle-wave duality

11
1.4 1.3. Uniqueness and role of quantum
Origin and Development of Quantum Mechanics
physics

In quantum mechanics every moving object in the universe has both particle like
and wave like properties. Both radiation (wave) and matter (particle) exhibit wave
like property uncertain situations and particle like properties in others called Wave
particle duality. Light is described by electromagnetic waves or particles (photons).
Interference and diffraction phenomena implies that light has a wave like property
while photoelectric and compton effects indicates that light has particle like nature.
De Broglie assigned wave properties to particles called matter waves. So any moving
object has particle-wave nature.

2. Quantum states are discrete

In classical physics ,the state of the system at any time t is obtained by specifying
its position and momentum of all the constituents of the system. However,in quan-
tum mechanics, a system cannot be described by a full specification of its coordinates
and momenta due to uncertainity principle. In other words, we cannot measure both
the position and momentum of a particle with unlimitted precision simltaneously.
Hence such particles are best described by their wave functions which satisfy cer-
tain boundary conditions imposed by the container to which they are contained. In
quantum mechanics physical quantities are observables that exist in discrete. Beam
of light can only have integral multiples of photons.That is n = 1, 2, 3,...... but not n =
0.3, 1.5, 1.9; 2.3 An electron in an atom can only have a discrete energy values.

3. Probabilistic nature of phenomena

A quantum mechanical system is described by a wave function of certain vari-

ables.This function contains all information about the system or the event at some
position in space , in a certain state of energy and time when physists use Quantum
mechanics to predict the result of an experiment. The only thing they predict is the
probability of detecting each of the possible out comes. Hence, Quantum mechanics
is probabilistic.

4. Quantum mechanics is not a magic

The core principle of physics are still intact. Mass-energy is still conserved, en-
tropy still increases and nothing can move faster than light. One cannot exploit quan-

12
1.4 1.3. Uniqueness and role of quantum
Origin and Development of Quantum Mechanics
physics

tum effects to build a perptual motion machine.

5. The correspondence principle This principle states that quantum results must
correspond to those obtained from classical physics in the limit of large quantum
number. In other words, Classical mechanics is the special case of quantum me-
chanics. The classical sizes for length, mass and time are on the order of cm; gm and
sec and typically involve large quantum numbers. As n −→ ∞[Quantum Mechanics]
−→[Classical Mechanics], n=typical quantum number.

13
 2

Mathematical development of quantum mechanics

2.1 Measurments and observables

Observables

An observable is a dynamical variable that can be measured. The dynamical vari-

ables in physics are position,velocity, linear momentum, angular momentum and
energy.

Operators

Are non-comutative dynamical variables. For any two operators A and B, AB 6=

BA but for any two c-number (not operators) observables C and D, CD = DC. In
quantum mechanics, the dynamical variable (observables) like position,linear mo-
mentum p, angular momentum L, and energy E have corresponding non-comutative
dynamical variables called operators. Table 2.1 : Observable and the corresponding
Operators
2.1 Measurments and observables
Mathematical development of quantum mechanics

No Observable Operator
1 X X̂
2 V vop
3 P P̂
4 L L̂
5 E Ê
6 H Ĥ

The operators P̂ and Ê are differentiation operators.P̂ = −ı~∇, for one dimen-
sion, Pˆx = −ı~ ∂x
∂
, Pˆy = −ı~ ∂y
∂
and Pˆz = −ı~ ∂z
∂
.

vop = − ı~∇
m

∂
Ê = −ı~ ∂t
P2
The hamiltonian (total energy)of the system is H = KE + U = 2m
+ V (r) and the
~2
hamiltonian operator Ĥ = − 2m ∇2 + V̂ (r)

Measurement in Quantum Mechanics Quantum theory is about the results of

measurement. It says nothing about what might happen in the physical world out
side the context of measurement, the emphasis is on measurement. In classical physics
it is possible to perform measurement on a system with out disturbing it significantly.
But in quantum mechanics, the measurement process perturbs the system signifi-
cantly. In other words, a measurement always causes the system to jump into an
eigenstate of the dynamical variable that is being measured. For instance, to mea-
sure the position of a hydrogenic electron, we need to bombard the electron with
electromagnetic radiation (photon). If we want to determine the position accurately,
the wave length of radiation must be sufficiently short. As the electron orbit is in the
order 10−10 m we have to use a radiation whose wavelength is smaller than 10−10 m
which means we need to bombard the electron with photons of energies higher than

hc
E = hν = ≈ 104 eV (2.1)
λ

when such photon strike the electron, not only with they perturb, they knock it

15
2.2 Uncertainty principle Mathematical development of quantum mechanics

completely off its orbit. Recall that the ionization energy of the hydrogen atom is
13.6eV . The act of measurement in quantum mechanics generally changes the state
of the system.

2.2 Uncertainty principle

2.2.1 Wave packet

De Broglie attached wave property to particles. E = hν, p = ~k, these are true for
photons but by de Broglie, they must be true for particles. We can assign a plane
wave every particle.

ψ(r, t) = Aeı(κr−ωt) (2.2)

is plane wave propagating along the x-axis. The wavelength of these plane wave is

2π h h
λ= = = (deBroglie) (2.3)
κ p mv

The particle must be sufficiently small to generate a measurable wavelength or wave

character appears in atomic region. Phase of the wave if κr − ωt

d
(κr − ωt) = 0 (2.4)
dt

dr
κ −ω =0 (2.5)
dt

ω
vκ = ω, v = (2.6)
κ
is the phase velocity of the wave. If we want to describe a particle as spatially limited
entity, we cannot describe it by a plane wave. Instead, we try to describe the particle
by a finite wave packet. A wave packet is superposition of harmonic waves differing
in wavelength and phase velocity.
Z κ0 +∆κ
ψ(r, t) = C(κ)eı[κr−ω(κ)t] dκ, (2.7)
κ0 −∆κ

16
2.2 Uncertainty principle Mathematical development of quantum mechanics

2π
Fourier integral. where ω(κ) is the angular frequency as a function of κ, κ0 = λ0
is
mean wave number of the group. ∆κ measure of extension (frequency spread,∆κ 
κ) and C(κ) the amplitude is slowly varying function of κ in the integration interval
∆κ.Up on expanding the frequency ω(κ) using Taylor’s series as

dω d2 ω
ω(κ) = ω(κ0 ) + (κ − κ0 ) |κ=κ0 +(κ − κ0 )2 2 |κ=κ0 = ω0 + (κ − κ0 )vg (2.8)
dκ dκ
dω
where, vg = dκ
the group velocity and ω0 = ω(κ)
Z κ0 +∆κ
ψ(r, t) = C(∆κ + κ0 )eı[(∆κ+κ0 )r−(ω0 (κ−κ0 )vg )t] dκ, (2.9)
κ0 −∆κ

let κ − κ0 = ∆κ = η, dκ = dη.

ψ(r, t) = eı(κ0 r−ω0 t) C(r, t) (2.10)

Where,C(r, t) = 2C(κ0 ) sin(∆κ(r−v

r−vg t
g t))
The presence of small quantity ∆κ in C(r, t) im-
plies that C(r, t) varies only slowly depending on x and t. We can regard C(r, t) as the
amplitude of an approximate monochromatic wave and κ0 r − ω0 t as its phase. let
∆κ(x − vg t) = z
sin z
C(x, t) = 2C(κ0 )∆κ (2.11)
z
sin z sin z
Variation in amplitude is determined by the factor z
limz→0 z
= 1 for z = 0 and
0 for ±π, ±2π, ..... Superposition generates a wave packet whose amplitude is non-
sin z
zero only in finite region and it is described by z
The wave packet is entirely lo-
cated between two points say −π to π. We can localize the position of a particle in a
particular description. Localization in time Putting t =0,

∆κx − 0 = z (2.12)

∆κ∆x = ∆z = 2π (2.13)

Using for the relation of λ and κ we have that

∆p∆x = h (2.14)

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2.2 Uncertainty principle Mathematical development of quantum mechanics

The unertainity relation for position and momentum called Heisenberg’s uncertain-
ity relation. A state cannot be prepared in which both the position and momentum of
a particle can be determined simultaneously to arbitrary accuracy or the act of mea-
suring the position of the particle forces the system into a state in which the momen-
h
tum is no longer known exactly but has become uncertain by an amount ∆p = ∆x
,
similarly the more precisely the momentum of the system is known, the greater the
range of the result in position measurement. The above restriction is on ”comple-
mentary” pairs ∆px ∆x = h, ∆py ∆y = h and ∆pz ∆z = h.

Localization in space putting x=0,

0 − ∆κvg t = z (2.15)

∆κvg ∆t = ∆z = 2π (2.16)

dω
where as vg = dκ
and E = ~ω
∆E∆t = h (2.17)

is energy-time uncertainity. In order to know precisely when the wave is at a given

point ∆t , then we must have a large range of E. We can also show that the total
angular momentum J and the angular displacement θ has the same uncertainity re-
lation ∆J∆θ = h.

To sum up Heisenberg’s uncertainity principle which is a direct consquence of

dual nature of matter states that it is impossible to measure two cannonically con-
jugate physical quantities like position and momentum, energy and time, angular
momentum and angle θ whose product has a dimension of action (Joule-seconds).
The exact statment of the principle states that the product of the uncertainities in de-
termining the position and momentum, energy and time, angular momentum and
angle θ of a particle can never be smaller than the number of order of ~2 .

~
∆P ∆X ≥ (2.18)
2

18
2.3 The Concept of State Mathematical development of quantum mechanics

~
∆E∆t ≥ (2.19)
2

~
∆J∆θ ≥ (2.20)
2

2.3 The Concept of State

For a classical system the state of a system at any time t is obtained by specifying
its position and momentum of all the constituents of the system. But in quantum
mechanics, the state of a system cannot be described by specifying its position and
momentum due to the uncertainty principle. State in microword is connected to
the act of measurement whose result is determined by experiment or results can be
exactly predicted , measurement can be predictable or probabilistic. The state of
the quantum system is described by a wave function denoted by ψ(r, t) and every
information about the particle in the system is contained in the wave function by
schrodinger. ψ is the called the parameter, (r, t)is the argument. ψ(r, t) is called the
characteristic equation or the eigen function of the parameter set.

2.4 Superposition Principle

For an ensemble,if one possible state of the ensemble is described by ψ1 and another
possible state is described by ψ2 , then any linear combination (superposition) of ψ1
and ψ2 as

ψ = c1 ψ1 + c2 ψ2 (2.21)

where c1 and c2 are certain constants, is also a wave function describing the possible
state of the ensemble. In other words, any general state of an ensemble is represented
by the superposition (linear combination of ) of basis states. Note that in classical
mechanics, superposition characteristic of the resultant is entirely different from the
components unlike the quantum superposition.

19
2.5 Wave functions and physicalMathematical development of quantum mechanics
interpretation

2.5 Wave functions and physical interpretation

Quantum mechanically, the physical condition or state of a particle is described by a
wave function ψ which is a function of position and time . ψ = ψ(r, t). The wave func-
tion though itself has no physical interpretation yet it contains all relevant informa-
tion about the physical state of particle and thus describes it complectly. These wave
functions are usually complex with both real and imaginary parts. ψ = A + iB with
complex conjugate ψ ∗ = A − iB. The quantity ψ ∗ ψ is physically meaningful quan-
tity and ψ ∗ ψ = |ψ(r, t)|2 which defines the probability density. So ψ ∗ ψ = |ψ(r, t)|2 =
A2 + B 2 which is real and positive satisfying the normalization condition.

Z ∞
|ψ(r, t)|2 dv = 1 (2.22)
−∞

This has the meaning that the particle exists somewhere in space at all the times. If
R∞
−∞
|ψ(r, t)|2 dv = 0, the particle is nowhere in space all the times. A wave function
would be well behaved or admissible as a mathematical representation of state of a
particle if and only if it satisfies the following conditions

i) ψ must be finite to avoid infinite probability, continuous and single valued every
where to avoid multiple probability.
∂ψ ∂ψ ∂ψ
ii) , ,
∂x ∂y
and ∂z
are continuous and single valued every where.

iii) ψ must be normalized. For this ψ must go to 0 as x −→ ±∞, y −→ ±∞, z −→

R
±∞ in order that |ψ(r, t)|2 dv over all space be a finite constant.

2.6 Expectation value of dynamical variables

To each physical observable in particular state of a dynamical system, we can assign
(classically) a particular mathematical variable such as position, energy and momen-
tum due to the fact that all physical observable have definite values in classical states.
But in quantum mechanics, the statistical interpretation of wave functions describ-
ing dynamical state of a system implies the uncertainty in the measurement of any

20
2.6 Expectation value of dynamical
Mathematical
variables development of quantum mechanics

two canonically conjugate observable. Thus we talk of expectation values of opera-

tors assigned to any physical observable in quantum mechanics.

The wave function ψ has probabilistic interpretation, therefore it is essential to

calculate the expectation or average value of dynamical variable (quantity) defined
by wave function. In physics such dynamic quantities are space-coordinates, mo-
mentum and energy of the system. The expectation or average value of dynamical
quantity is the mathematical expectation of for the result of a single measurement.
In other words, it can be defined as the average of the result of large number of mea-
surement on independent systems. The expectation or average value of any quantity
h(r) which depends on position, for a normalized wave function ψ can be written as
Z Z
hh(r)i = p(r, t)ĥ(r)dτ = ψ ∗ ĥ(r)ψdτ (2.23)

where ĥ(r) is the operator associated with dynamical quantity h(r): The mean value
of position r is Z
hri = ψ ∗ r̂ψdτ (2.24)

are the expectation value of the coordinates r of position of particle. see also that
Z
hr i = ψ ∗ r2 ψdτ
2
(2.25)

Example 1. A particle constrained to x-axis has a wave function ψ(x) = ax between x

= 0 to x = 1 and ψ = 0 every where, for a is a normalization constant.

i). Find a ii). Find hxi iii). the uncertainty or deviation in x(∆x)

solution

i) From the normalization condition

Z ∞
|ψ(x)|2 dx = 1 (2.26)
−∞
Z 1
a2 x2 dx = 1
0

as ψ = 0 any where other than 0 ≤ x ≤ 1

Z 1
2
a x2 = 1
0

21
2.7 Probability density Mathematical development of quantum mechanics

√
,a= 3

ii) Z
hxi = ψ ∗ x̂ψdx (2.27)
Z 1 √ √
= 3xx̂ 3xdx
0
x4
= 3 4 |10 = 0.75

iii) the uncertainty or deviation in x(∆x) is given as

p
∆x = hx2 i − hxi2 (2.28)

The final result for the uncertainty is ∆x = 0.194 ≈ 0.2 Problem 1:- A certain particle
x2
particle is described by a normalized wave function ψ(x) = N e−( 2a )+ikx . then find the
expectation value of the particle’s A. position B. momentum

2.7 Probability density

Consider an ensemble where each system carrying of a single particle moving un-
der the action of some given force. Let the wave function describing the system be
ψ(r, t). Physical quantities like position, momentum and energy will not be the same
for every system. There is a distribution of these numbers which can be described by
a probability function. For example, position is uncertain by an amount of order of
the linear dimension of the wave function. We can regard as a measure of finding the
probability of a particle at a particular region. ψ is a complex function but probability
is real and positive. The product of ψ and its complex conjugate ψ ∗ (ψψ ∗ ) is called the
probability density (p(r, t)).

p(r, t) = ψψ ∗ = |ψ(r, t)|2 (2.29)

p(r, t)d3 r is the probability of finding a particle with in the volume element d3 r =
dxdydz about the point r = (x, y, z) at the time t. The probability of finding the particle
between two points x1 = a and x2 = b is given by
Z b
pab = |ψ(r, t)|2 dx (2.30)
a

22
2.7 Probability density Mathematical development of quantum mechanics

The probability of finding the particle must be unity, hence the wave function ψ(r, t)
must be normalized which means mathematically
Z
|ψ(r, t)|2 d3 r = 1 (2.31)
overthewholespace

A wave functions whose integral is finite are called square integrable. such functions
R
can be normalized in multiplying by an appropriate constant as a|ψ(r, t)|2 d3 r = 1,
where a is called the normalization constant given by

1
a= R (2.32)
a|ψ(r, t)|2 d3 r
√
Example 2:- Consider a particle whose normalized wave function is ψ(x) = 2α αxe−αx
for x ¿ 0 and 0 for x ¡ 0. what is the

a) probability density. b) probability of finding the particle between the points

1
x1 = 0 and x2 = α

Solution
√ √
Given ψ(x) = 2α αxe−αx , ψ ∗ (x) = 2α αxe−αx

a) The probability density is

ρ(x) = ψ ∗ (x)ψ(x) = 4α3 x2 e−2αx (2.33)

b) Z b
pab = |ψ(x, t)|2 dx (2.34)
a
Z 1
α
p0 1 = 4α3 x2 e−2αx dx
α
0

let
y dy
2αx = y, x = , dx =
2α 2

Z 2
1 1
p0 1 = y 2 e−y dy = 1 − = 0.3234
α 2 0 e2

23
 3

Operator Algebra

3.1 Vector Space and Hilbert Space

3.1.1 Linear Vector Space

A linear vector space consists of two sets of elements and two algebraic rules. That
is a set of vectors ψ; φ; ϕ.... and a set of scalars a, b, c,.... together with rule of vector
addition and rule of scalar multiplication. Addition rule of vectors has the properties
and structure of an abelian group.

1. If and ψ and φ; are vectors of a space, their sum or elements of vector space is
also an element of the vector space.

2. vector addition is commutative, ψ + φ = φ + ψ.

3. vector addition is associative, ψ + (φ + ϕ) = (ψ + φ) + ϕ.

4. vector addition has additive or symmetric inverse such that for each vector ψ
must have a symmetric vector −ψ such that ψ+−ψ = −ψ+ψ = 0 and additive identity
ψ + 0 = 0 + ψ = ψ.

Multiplication rules 1.The product of a scalar with a vector give an other vector.
For two vectors ψ and φ in the vector space , any linear combination aψ + bφ,a and b
are any scalars, is also a vector space of the same vector space.
3.1 Vector Space and Hilbert Space Operator Algebra

2. multiplication of a vector by a scalar is distributive over addition. a(ψ + φ) =

aψ + aφand(a + b)ψ = aψ + bψ

3. multiplication of a vector by a scalar is associative. a(bψ) = (ab)ψ

4. multiplication of a vector by a scalar has multiplicative identity. Iψ = ψI = ψ

5. multiplication of a vector by zero produce a null vector. 0ψ = ψ0 = 0.

3.1.2 Hilbert Space

A space consists of vectors ψ, φ, ϕ.... and a set of scalars a, b, c,.... which satisfy the
following properties.

1. Hilbert Space is linear.

2. Hilbert Space has a definite inner or scalar product which is strictly positive.
The scalar product of an element with an other element φ is generally complex num-
ber denoted by (ψ, φ) = ψ ∗ φ and (φ, ψ) = φ ∗ ψ, so (ψ, φ) = (φ, ψ). In general,
(ψ, φ) = (φ, ψ)∗.

3. (aψ, bφ)= a ∗ bψ ∗ φ = a ∗ b(ψ, φ)

(φ, aψ1 + bψ2 ) = (φ, aψ1 ) + (φ, bψ2 )

4. (ψ, ψ) = k ψ k2 ≥ 0, f orψ 6= 0

3.1.3 Dirac Notation

The physical situation or state of a system is represented by elements of a Hilbert

space. These elements are called state vectors. We can represent the state vectors
in different bases by means of function expansion. A vector can be equivalently ex-
pressed by its components in cartesian, cylinderical or spherical polar coordinate
systems. The meaning of a vector is independent of the coordinate system chosen
to represent its components. Similarily a state in microscopic system has a mean-
ing independent of the basis in which it is expanded. Dirac introduced the bra-ket
notation in quantum mechanics which allows one to manuplate the formalism of

25
3.2 Adjoint and Hermitian operator Operator Algebra

quantum mechanics with ease and clarity. kets are elements of a vector space. Dirac
denoted the state vector ψ by the symbol |ψi which is called a ket-vector or simply a
ket. Kets blong to the vector (Hilbert) space or to the ket-space.Kets can be expressed
as column matrix. Bras are elements of a dual (complex conjugate) space.Dirac de-
noted the element of the dual space by the symbol h| which is called bra-vector.

The scalar or inner product has two physical meanings

1. (ψ, φ) = hψ|φi denotes the projection of |ψi on |φi like dot product of two clas-
sical vectors A.B = A cos θB is projection of A on B.

2. (ψ, φ) = hψ|φi is the probability amplitude that a system is state |ψi will be
found in state φ after measurement.

3.1.4 Superposition Principle

Any general ket(bra) vector is represented as superposition of basis kets(bras), due to

the linearity property of quantum mechanics. Any ket or any linear combination of
kets also define the state of the system independently and completely.

3.1.5 Eigenvalue and Eigenfunctions

The results of operation on a vector with an operator A is in general a different vector,

but there may be some vector |ψi with the property that operating by A on it yields
the same vector |ψi multiplied by a scalar α

A|ψi = α|ψi

This is called eigenvalue equation for operator A with an eigenvalue α and an

eigenfunction or eigenstate |ψi.

3.2 Adjoint and Hermitian operator

The inner product of two square integrable functions ψ and φ is defined as (ψ; φ) =
R ∗
ψ φdv. Adjoint of the operator A(A+ ) is defined by the relation

26
3.3 Fundamental postulates of quantum mechanics Operator Algebra

(ψ, Aφ) = (A+ ψ, φ)

Properties of adjoint operators

1. The adjoint of (CA) = C + A+ where C is complex number.

2. (AB)+ = B + A+

3.(ABCD)+ = D+ C + B + A+

An operator A is said to be hermitian if it is equal to its adjoint operator or if it is

self adjoint, A = A+ :

property of hermitian operator

1. Eigenvalue of hermitian operator is real.

2. Eigenfunctions corresponding to different eigenvalues are orthogonal.

3.3 Fundamental postulates of quantum mechanics

1.Observable quantum mechanical quantities are described by Hermitean operators
 on the Hilbert space H.

A|αn i = an |αn i

2. Any classical physical quantity must be a function of a pair of canonically con-

jugate variables.The corresponding quantum mechanical operators are obtained by
replacing their counter parts.

3. [qi , qj ] = [pi , pj ] = 0 but the commutator of [qi , pj ] = i~δih .

4. The state of a system, at any time t, is exhaustively characterized by a vector

|ψ(t)i of Hilbert space up on which the operator corresponding to an observable act.
|ψ(t)i contains all information about the system and any superposition of state vec-
tors.

27
3.3 Fundamental postulates of quantum mechanics Operator Algebra

X
|ψ(t)i = ai |ψi (t)i

5. Actual measurement of a physical observable carries over the state vector of a

system into which an eigevector of the observed quantity.

6. If at the instant of measurement , the state of a system is one of the state vectors,
then the results of measurement will certainly be the corresponding eigenvalue.

7. In general measurement of physical observable does not lead with certainty to

a definite value. As the result we talk about expectation values.

8. In the course of time development the normalization of the state of a system

does not change.

9. The time evolution of the quantum state of an isolated quantum mechanical

∂
system is determined by the Schrodinger equation i~ ∂t |ψ(t)i = Ĥ(t)|ψ(t)i

10. For a system of identical particles, state vectors are either completely symmet-
ric or anti-symmetric.

28
 4

Schrodinger and Heiseberg Equation

ψ(r, t) represents a particle of undetermined position travelling in the positive x-

direction with precisely known momentum p and kinetic energy E 0 . p = ~ω, E 0 =
2π
~κ, κ = λ
and ω = 2πν. ψ(r, t) is expected to have one of the following form or
combination of them.

cos(kx − ωt), sin(kx − ωt), ei((kx−ωt)) , e−i((kx−ωt))

These equations are from the experiments like those of Davinson and Germen and of
Thomsen. Classical wave equation

∂2 1 ∂2
W = W
∂x2 V 2 ∂t2

where W = W (x, t) wave function of the particle , v = λν is the speed of the

particle.
2m(E−U )
∇2 ψ(x) + ~2
ψ(x) = 0 is the time independent schrodinger equation for a
particle moving in a potential U.

P = ~ω, E 0 = ~κ and ψ(x, t) = Aei(kx−ωt) is plane wave equation for a free particle.
−~2 ∂ 2
As finally, we have that 2m ∂x2
ψ = i~ ∂ψ
∂t
is the time dependent schrodinger equation
4.1 solution of schrodinger equation Schrodinger and Heiseberg Equation

for a free particle. In three dimensions the only difference is (x, y, z, t).

4.1 solution of schrodinger equation

The time-dependent schrodinger equation, unlike the time-independent one, is not
an eigenvalue equation or it is not an equation that has only solutions for a partic-
ular set of values of some parameters. In fact,it is quite possible to have any spatial
function as a solution of the time-dependent schrodinger equation at a given time.
That spatial function also determines exactly how the wave function subsequently
will evolve in time. This is done with the condition that the potential as a function
of space and time is known. Though this ability to predict the future behavior of
the wave function ,with defined value of potential, is a rather important property of
the time-dependent schrodinger equation, here after we are going to consider differ-
ent potentials (one dimensional potentials, Free particle (Zero potential), potential
step, Potential Hill or Barrier, infinite well potential)to and a solution for the time
independent schrodinger equation.

4.2 schrodinger
In quantum mechanics , a state function is a linear combination(superposition) of
eigenstates . In Schrodinger picture the state of a system evolves with time while the
operators are stationary. The evolution for a closed quantum system is brought by
a unitary operator called Time-evolution operator. The state of a system evolves in
time according to Schrodinger equation.

d
i~ |ψ(t)i = H|ψ(t)i
dt

4.3 Heisenberg picture

Heisenberg picture is the formulation of quantum mechanics where the operators
(observables and others) are time-depenedent and state vectors are time-independent.
dA(t)
The state vector |ψ(t)i remain constant in time but an observable A satisfies dt
=

30
4.3 Heisenberg picture Schrodinger and Heiseberg Equation

1
i~
[A(t), H] + ∂A
∂t
In some senses, Heisenberg picture is more natural and fundamental
than the Schrodinger picture, especially for relativistic theories. otherwise the two
pictures only differ by a time-dependent basis change. but the measurement statis-
tics are the same in both pictures as they should be.

31
 5

The harmonic oscillator

The simple harmonic oscillator plays an amazingly important role in many areas of
quantum physics. It is another example of a one-dimensional bound particle, we
consider the simple harmonic oscillator.The name simple harmonic oscillator (or
SHO) is used in classical and quantum mechanics for a system that oscillates about a
stable equilibrium point to which it is bound by a force obeying Hookes law,Familiar
classical examples of harmonic oscillators are a mass suspended from an ideal spring
and a pendulum oscillating with small amplitude. An important example of a quan-
tum harmonic oscillator is still the motion of any one atom inside a solid crystal; each
atom has a stable equilibrium position relative to its neighboring atoms and can os-
cillate harmonically about that position. Another important example is a diatomic
molecule, such as HCl,whose two atoms can vibrate harmonically, in and out from
one another. We can find asymptote solution of one dimension schrodinger equa-
tion, and zero point energy using harmonic oscillator.

5.1 Correspondence principle

What is the connection of the quantum harmonic oscillator with that of classical me-
chanics? The quantum result approaches the classical result in limit of n −→ ∞ It is
easy to show that for classical harmonic oscillator
5.2 Time evolution operators The harmonic oscillator

1
ρ(x) = √
π A2 − x 2
where A are the turning points. The quantum result, the probability density, ρ(x) =
|ψn (x)|2 for large n takes similar shape except for the nodes, which are practically
invisible on the macroscopic scale. We can express harmonic oscillator interms of
creation and annihilation operators.

5.2 Time evolution operators

Time-evolution and conservation laws As well as determining which operators are
complementary, the commutator of two operators also plays a role in determining
the time-evolution of systems and in particular the time-evolution of the expectation
values of observables. The precise relation for operators that do not have an intrinsic
dependence on the time (in the sense that ∂A
∂t
= 0) is

∂A
i~ = [A, H]
∂t
We see that if the operator for the observable commutes with the hamiltonian,[A, H] =
0 then the expectation value of the operator does not change with time. An observ-
able that commutes with the hamiltonian for the system, and which therefore has an
expectation value that does not change with time, is called a constant of the motion,
and its expectation value is said to be conserved. We need explicit form of X(t) and
px (t) for a harmonic oscillator.

5.3 Question to practice for exit exam competence

1.In quantum mechanics,the state of a system cannot be described by

A. Its position

B. Its momentum

C. All the constituents of the system

33
5.3 Question to practice for exit exam competence The harmonic oscillator

D. A and B

2. Which one of the following is true the wave function for physical state of particles
−−−−−−−−−−−−−−−−

A. Contains all relevant information

B. must be finite

C. must be normalized

D. All of the above

3. A particle constrained to y-axis has a wave function ψ(y) = by particle is satisfied

between y = 0 and y = 1.

A. the value of b

B. the hyi and hpi

x
4. A certain particle is described by a normalized wave function ψ(x) = Ae 2a −ikx A)
Find the expectation value of the particles position

B) The expectation value of the particles momentum

C) Uncertainty of position and momentum

5. Consider a particle whose normalized wave function is ψ(x) = 2αxeαx for x > 0
and 0 for x < 0.

A) what is the probability density.

B) What is probability of finding the particle between the points x1 = 0 and x2 = α1 .

x
6. A certain particle is described by a normalized wave function ψ(x) = Ae 2a −ikx

A) Find the expectation value of the particles position

B) The expectation value of the particles momentum

C) Uncertainty of position and momentum

34
5.3 Question to practice for exit exam competence The harmonic oscillator

7. Consider a particle whose normalized wave function is ψ(x) = 2αxeαx for x > 0
and 0 for x < 0.

A) what is the probability density.

B) What is probability of finding the particle between the points x1 = 0 and x2 = α1 .

8. Particle of mass m is in the potential well V (x) = 0 0 ≤ x ≤ a and V (x) = ∞

otherwise. Find A) The normalised wave function describing the particle.

B the energy eigenvalue.

C the probability of finding the particle from x1 = 0 to x2 = a2 ?

9. A particle of mass m is in the state ψ(x, t) = Aeαmx+iωt where A and α are positive
real constants.find A) the normalization constant A and the probability density.

B hxi, hx2 i, hpi, and hp2 i

−i~
d
ψ ∗ ∂x
∂
R
C velocity of the particle (v = dt
hxi = m
ψdx)

D ∆x and ∆p

E Is ∆x∆p consistent to the uncertainty relation?

10. For three normalized waves ψ1 (x, t) = Aei(kx−ωt) , ψ2 (x, t) = Ae−i(kx+ωt) ,

ψ3 (x, t) = −Ae−i(kx+ωt) . Using superposition principle show that

A ψ1 (x, t) + ψ2 (x, t) =A cos kxe−iωt

B ψ1 (x, t) + ψ3 (x, t) =2iA sin kxe−iωt

11. A particle in a simple harmonic oscillator is described by the wave function

ψ(x, t) = 10cm cos(4π + 2πt). then find A. Êψ(x, t) B. p̂ψ(x, t), and C. Ĥψ(x, t)

12. Discuss and write the harmonic oscillator in terms of creation and annihilation.

13. Show and discuss the mean value kinetic energy and potential energy are equal
and are half of the total energy of a harmonic oscillator.

14. The state of a particle moving in a one- dimensional harmonic oscillator is given
by

35
5.3 Question to practice for exit exam competence The harmonic oscillator

r
1 3 2 3
|ni = √ |0i + √ |1i − √ |2i − |3i
17 17 17 17

where |ni represents the normalized eigenstate,find

A. hN i and hHi

B. hxi and hpi

C. what is the probability of finding the oscillator in the ground state, first exited
state, and in the third exited state

15. Show that for any energy eigenstate |ni of a harmonic oscillator ∆x∆p = (n + 12 )~

16. Using the time-dependent Schrodinger equation and its complex conjugate
show that the rate of the expectation value of momentum is the net force.

36