Dr. Dwi Hudiyanti, MSc.

085225064261
tugaskimiadwi@gmail.com

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Syllabus and Reference
Syllabus:
 Quantum Theory: Introduction and Principles
 Quantum Theory: Techniques and Applications
 Atomic Structure and Spectra
 Molecular Structure

Reference:
 Atkins, P. & de Paula, J., 2006, Physical Chemistry, 9th
ed., Chap. 7-10th , W. H. Freeman and Company, New
York

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Tasks, Assessments n Grading
 Tasks: >>> tugaskimiadwi@gmail.com
 email subject & filename in attachment : KF3 <tugas> Name &
NIM
 Quiz
 Problem solving
 paper

 Assessment:
 UTS
 UAS

 Grading:
 Tasks 20%
 UTS 40%
 UAS 40%

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The origin of quantum mechanics
 Classical mechanics: Isaac Newton
 Trajectory, location, and momentum in each instant are
exactly predicted
 Excitation to any energy
 Big objects and energies
 Light is electromagnetic radiation >>>
 electromagnetic field: an oscillating electric and magnetic
disturbance that spreads as a harmonic wave

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  electromagnetic field: two
components
 electric field that acts on
charged particles (whether
stationary of moving)
 magnetic field that acts only
on moving charged particles
 wavelength,λ (lambda), the
distance between the
neighbouring peaks of the
wave
 frequency, ν (nu), the
number of times per second at
which its displacement at a
fixed point returns to its
original value

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The quantum mechanics
 Quantum mechanics:
 Particle>>> may not have an arbitrary energy
 Particle and wave blend together (particle and wave
dualism)
 All the properties of a system express in terms of a
wavefunction, obtained by solving Schrödinger eq.
 Uncertainty principle
 Small objects and energies

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Energy quantization
 Black body radiation
 Ultraviolet catastrophe >>>> e.m. field take up energy
only in discrete amounts
 Heat capasities
 >>> Vibration of atoms take up energy only in discrete
amounts
 Atomic and molecular spectra
 >>> take up energy only in discrete amounts

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Black-body radiation
A hot object emits e.m radiation: T, 

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Black-body radiation
Lord Rayleigh:
• Energy density
• the electromagnetic field
>> a collection of
oscillators of all possible
frequencies.
• radiation of frequency ν
(and therefore of
wavelength λ = c/ν) >>>
electromagnetic oscillator
of that frequency had been
excited

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Black-body radiation
Max Planck
 the energy of each
electromagnetic oscillator
is limited to discrete
values and cannot be
varied arbitrarily >>>
quantization of energy
 Quantization reduces the
contribution from the high
frequency oscillators >>>
cannot be significantly
excited with the energy
available.

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Heat capacities
Dulong and Petit’s law
 the molar heat capacities of all monatomic solids are
the same and (in modern units) close to 25 J K−1 mol−1.
 classical physics: molar constant volume heat capacity

 But, at low temperatures: <3R, and that the values

approach zero as T→0. ?????

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Heat capacities
Einstein:
 each atom oscillated about its
equilibrium position with a
single frequency ν.
 Planck’s hypothesis >> the
energy of oscillation, confined
to discrete values, nhν, n is an
integer.

 a high frequency corresponds to

a high Einstein temperature

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Heat capacities
Debye formula:
 averaging over all the
frequencies

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Atomic and molecular spectra

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InterActivity
 Using eqn 7.11, plot CV,m against T for several values of
the Einstein temperature θE. At low temperature, does
an increase in θE result in an increase or decrease of
CV,m? Estimate the temperature at which the value of
CV,m reaches the classical value given by eqn 7.10.

 Starting with the Debye formula (eqn 7.13), plot

dCV,m/dT, the temperature coefficient of CV,m, against T
for θD = 400 K. At what temperature is CV,m most
sensitive to temperature?

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Wave-particle duality
 Electromagnetic radiation
 >>> wave-like (classical physic)
 >>> particles, photons (quantum mechanics)

 Electrons
 >>> particles (classical physic)
 >>> wave-like (quantum mechanics)

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Particle character of
electromagnetic radiation
 Electromagnetic radiation, freq= 
 >>> energy: 0, h, 2h, ….
 >>> suggest: consist of 0, 1, 2, …. particles, each has
energy h >>> photons

 Dicrete spectra atoms or molecules >>> atoms or

molecules generate photon when discharge energy E
(E = h)

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Photoelectric effect
 Experimental evidence of photons
1. No electrons are ejected, regardless of the intensity
of the radiation, unless its frequency exceeds a
threshold value characteristic of the metal.
2. The kinetic energy of the ejected electrons increases
linearly with the frequency of the incident
radiation but is independent of the intensity of the
radiation.
3. Even at low light intensities, electrons are ejected
immediately if the frequency is above the
threshold.
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  photoelectric effect depends on the ejection of an
electron when it is involved in a collision with a
particle-like projectile that carries enough energy to
eject the electron from the metal
 projectile is a photon of energy hν
 the kinetic energy of the ejected electron ( ½mev2)
 The conservation of energy

1. Photoejection cannot occur if hν <Φ because the photon brings

insufficient energy.
2. the kinetic energy of an ejected electron should increase linearly
with frequency.
3. When a photon collides with an electron, it gives up all its energy,
so we should expect electrons to appear as soon as the collisions
begin, provided the photons have sufficient energy.
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The wave character of particles
 Diffraction is the
interference caused by
an object in the path of
waves.
 constructive or
destructive  a region of
enhanced or diminished
intensity of the wave.
 Particles have wave-
like properties

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Modern physics:
 On an atomic scale
 the classical concepts of particle
and wave melt together,
 Particles taking on the
characteristics of waves, and
waves the characteristics of
particles.
 de Broglie relation
 any particle, not only photons,
travelling with a linear
momentum p =mv (with m the
mass and v the speed of the
particle) should have in some
sense a wavelength

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  Macroscopic bodies  high momenta (because their
mass is so great), even when they are moving slowly,
that their wavelengths are undetectably small, and the
wave-like properties cannot be observed.
 This undetectability is why, in spite of its deficiencies,
classical mechanics can be used to explain the
behaviour of macroscopic bodies. It is necessary to
invoke quantum mechanics only for microscopic
systems, such as atoms and molecules, in which
masses are small.

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  the energies of electromagnetic radiation and of
matter cannot be varied continuously,
 for small objects the discreteness of energy is highly
significant

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  Quantum mechanics acknowledges the wave–particle
duality of matter and the existence of quantization:
 particle is distributed through space like a wave.
 The mathematical representation of the wave that
replaces the classical concept of trajectory is called a
wavefunction, ψ (psi).

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The Schrödinger equation
 The Schrödinger equation is a second-order
differential equation used to calculate the
wavefunction of a system
 particle of mass m moving in one dimension with
energy E in a system that does not change with time
(for instance, its volume remains constant) is

 the linear momentum is related to the wavelength of

the wavefunction

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The Born interpretation
 The wavefunction contains all the dynamical information
about the system it describes.

 Max Born:
 the location of the particle
 focuses on the square of the wavefunction (or the square
modulus,
 |ψ |2 =ψ *ψ, if ψ is complex;
 |ψ |2 is the probability density
 The wavefunction ψ is the probability amplitude

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  Indirect significance,
because it gives rise to
the possibility of
constructive and
destructive interference
between different
wavefunctions (next
chapter)

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Normalization

A mathematical feature of the

Schrödinger equation is that,
if ψ is a solution, then so
is Nψ, where N is any
constant.

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Quantization
The Born interpretation puts severe restrictions on
the acceptability of wavefunctions
 The principal constraint is that ψ must not be
infinite anywhere. >>> rules out many possible
solutions of the Schrödinger equation
 the wavefunction must be singlevalued; that is, have
only one value at each point of space. >>it would be
absurd to have more than one probability

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 The Schrödinger equation:
a second-order
differential equation
 the second derivative of
ψ must be well-defined if
the equation is to be
applicable everywhere
 continuous
 have a continuous slope
 be single-valued
 be square-integrable

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  An acceptable wavefunction cannot be zero
everywhere
 Acceptable solutions of the Schrödinger equation do
not in general exist for arbitrary values of the energy E.
 a particle may possess only certain energies, for
otherwise its wavefunction would be physically
unacceptable.
 the energy of a particle is quantized

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Dwi Hudiyanti
The Schrödinger equation
 The Schrödinger equation for a particle of mass m free
to move parallel to the x-axis with zero potential
energy, V = 0,

solution
Pembuktian
The probability density
 Suppose that B = 0
 Where is the particle?

 probability density is independent of x, we cannot

predict where we will find it
 The same would be true if the wavefunction had A = 0
 suppose that in the wavefunction A = B

 the probability density periodically varies between 0

and 4|A|2
 The locations where the probability density is zero
correspond to nodes in the wavefunction.
Tugas: jelaskan mengapa ???
Operators, eigenvalues, and
eigenfunctions
Operator
form of
Schrödinger
equation

hamiltonian operator
Eigenvalue equation
The construction of operators

the operator
for location the operator for
linear momentum
parallel to the x-axis
 a sharply curved wavefunction
>> a high kinetic energy, a low
curvature >> a low kinetic
energy.
 consistent with the de Broglie
relation
 a particle to have a high kinetic
energy if the average curvature
of its wavefunction is high.
Locally there can be both
positive and negative
contributions to the kinetic
energy (because the curvature
can be either positive, ∪, or
negative, ∩), but the average is
always positive
Association of high curvature with
high kinetic energy
suppose we need to know
the wavefunction of a
particle with a given total
energy and a potential
energy that decreases
with increasing x
Hermitian operators
 Their eigenvalues are
real, and their
eigenfunctions are
‘orthogonal’.
 All observables have real
the position values (in the
operator (x ×) mathematical sense,
is hermitian such as x = 2 m and E =
10 J), so all observables
are represented by
hermitian operators.
orthogonal
 two different functions A general feature of
ψi and ψj are quantum mechanics:
orthogonal means that  that wavefunctions
the integral (over all corresponding to
space) of their product is different eigenvalues of
zero an hermitian operator
are orthogonal.
Superpositions and expectation
values
 the cosine wavefunction
linear momentum of the particle?
is a linear combination,
or sum, of eikx and e−ikx

not an eigenvalue equation  the total wavefunction is

a superposition of
 The property to which
more than one
the operator corresponds wavefunction
does not have a definite
value
  half the measurements
 repeatedly measured in a will show that the
long series of particle is moving to the
observations right and half the
 its magnitude will found
measurements will show
to be in all the that it is moving to the
measurements left
 the two component
wavefunctions occur
equally in the
superposition
 we cannot predict in which direction the particle
will in fact be found to be travelling; all we can say is
that, in a long series of observations, if the particle is
described by this wavefunction, then there are equal
probabilities of finding the particle travelling to
the right and to the left.
 the linear combination

 When the momentum is measured, in a single

observation one of the eigenvalues corresponding to
the ψk that contribute to the superposition will be
found.
 The probability of measuring a particular eigenvalue in
a series of observations is proportional to the square
modulus (|ck|2) of the corresponding coefficient in
the linear combination.
 The average value of a large number of observations is
given by the expectation value, Ω, of the operator
corresponding to the observable of interest.
The expectation value
 valid only for normalized
wavefunctions
 an expectation value is
the weighted average
of a large number of
observations of a
property.
The uncertainty principle
 It is impossible to specify  Heisenberg
simultaneously, with uncertainty principle
arbitrary precision, both
the momentum and the
position of a particle.
 if we know the position
of a particle exactly, then
we can say nothing about
its momentum.
The quantum mechanics
postulates
The quantum mechanics
postulates (2)