Quantum theory:

introduction and principles

 The origins of quantum
mechanics Classical physics fails to explain
microscopic phenomena as follows:
Classical Mechanics • Blackbody radiation
• Predicts a percise trajectory for particles • photoelectric effect
(specified location and momenta at each • Compton scattering
instant) • atomic stability
• atomic spectroscopy
• Allows translational, rotational, and vibrational
mode of motions to be exicited (control forced).
• Fail to extend to individual atoms, when
applied for transfering a very small energies,
and to very small mass object.
• Radiation is described in terms of oscillating
electromagnetic disturbance that spreads
through the vacuum at constant speed.
The origins of quantum mechanics

• The electromagnetic field classification

according to its frequency and
wavelength.
• Human eyes perceive different
wavelength radiation as various colors.
• White lights is micture all colors (380 electromagnetic field:
nm - 700 nm). - electric field (stationary or moving)
• A new view of light needs to be - magnetic field (stationary)
developed. λν=ϲ
The classification of the spectral regions ϲ = speed of light (m/s)
λ = wavelength (m)
ν = the frequency of cycles
per second (Hz/s-1).
ṽ = wavenumber (cm-1)
 Black-Body Radiation.
• A black body is an object that emits and
absorbs all the frequencies of the
radiation uniformly.
• A pinhole in an empty container at a
constant temperature is a good
approximation of a black body. Because
any radiation leaking out the hole has
been absorbed and re-emitted inside has
come to thermal equilibrium with the • The energy density increases in the
walls. region of shorter wavelength as the
temperature raised.
• The total energy density increases
with increasing temperature.
• This behavior is seen when a heated
iron bar glowing red hot becomes
white hot when heated further.
An opaque object emits electromagnetic radiation
according to its temperature
 Rayleigh-Jean’s law.
• where ρ (rho) ((J m−4), energy density, dE (J m−3),
• The energy density pν per unit frequency • k = Boltzmann’s constant (k = 1.381 × 10−23 J
interval at a frequency ν is, according to the K−1).
The Rayleigh-Jeans Radiation, • The total energy density in a region is obtained
by integrating eqn 8.3.
• dE = ρdλ, ρ = ......8.3 • although the Rayleigh–Jeans law is quite
successful at long wavelengths it fails badly at
short wavelengths. Thus, as λ decreases, ρ
increases without going through a maximum.
• a large amount of energy is radiated in the high-
• Although the Rayleigh- frequency region of the electromagnetic
Jeans law works for low spectrum, is called the ultraviolet catastrophe.
frequencies, it diverges at
high ν. • According to Classical physics, even cool objects
• This divergence for high should radiate in the UV and visible regions, so
frequencies is called the objects should glow in the dark; there should in
ultraviolet catastrophe. fact be no darkness.
 The Planck distribution On the basis of this assumption,
Planck was able to derive the
Planck distribution:
Max Planck explained the
blackbody radiation from the dE = ρdλ, ρ =
viewpoint of thermodynamics
in 1900. Assuming that the • For short wavelengths, hc/λkT
energies of the oscillations of
electrons which gave rise to >> 1 and ehc/λkT → ∞ faster than
the radiation must be λ5→ 0; therefore ρ → 0 as λ →
proportional to integral 0 or ν → ∞. Hence, the energy
multiples of the frequency. density approaches zero at high
The Planck distribution accounts
frequencies.
• For long wavelengths, hc/λkT very well for the experimentally
E = nhν, n = 0, 1, 2, . . . determined distribution of black-
<< 1, and the denominator in
body radiation. Planck’s
can be replaced by
where h is Planck’s constant ehc/λkT − 1= - 1 quantization hypothesis
essentially quenches the
contributions of high frequency,
short wavelength oscillators.
 Heat Capacities
• The French scientists Pierre-Louis Dulong and
Alexis Thérèse Petit determined the heat
capacities of a number of monatomic solids
• Classical physics predicts a constant value (25
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monoatomic solids.
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• Assumption of discrete energy levels (a Experiments at low

temperatures, however,
collection of harmonic oscillators) again led to a revealed that the molar
model that matched the experimental heat capacity approaches
observations (Einstein (1905)). zero when temperature
approaches zero.
 Atomic and molecular spectra • a molecule undergoes a

• Atomic and molecular spectra: Absorption spectroscopic transition, a change

and emission of electromagnetic radiation of state, when the Bohr frequency

(i.e., photons) by atoms and molecules

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occur only at discrete energy values.
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∆E = hν
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• Classical physics would predict absorption

be expressed in more words

or emission at all energies.

Spectroscopic transitions, such as

those shown above, can be accounted for if
we assume that a molecule emits a photon
as it changes between discrete energy levels.
Note that high-frequency radiation is
emitted when the energy change is large.
Wave–particle duality

The experimental evidence that led to the revision of two other basic
concepts concerning natural phenomena.
• The experiment shows that electromagnetic radiation, which classical
physics treats as wave-like, actually displays the characteristics of
particles.
• Another experiment shows that electrons—which classical physics treats
as particles—also display the characteristics of waves.
• Objects that are large in the absolute sense have the property that the
wavelengths associated with them are completely negligible compared to
their size. Therefore, large particles only manifest
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they never manifest their wave nature.

 Photoelectric Effect In the photoelectric effect, no
electrons are ejected when
the incident radiation has a
The experimental characteristics of the
frequency below a value
photoelectric effect are as follows: characteristic of the metal
• Threshold frequency depends on the properties and, above that value, the
of the metal. kinetic energy of the
• Instantaneous process. photoelectrons varies linearly
• Number of electrons ejected increases with the with the frequency of the
intensity of the light but does not depend on the incident radiation.
light’s frequency.
• KE of the photoelectrons depends on the
frequency but not on the intensity of the beam;
(a) The energy of the photon is
• KE of the photoelectrons increases linearly with
insufficient to drive an electron
the incident frequency. out of the metal.
(b) The energy of the photon is
The photoelectric effect is the ejection of electrons more than enough to eject an
from metals when they are exposed to ultraviolet electron, and the excess
radiation: energy is carried away as
= hν − Φ, where Φ is the work function, the energy the kinetic energy of the
required to remove an electron from the metal to photoelectron (the ejected
infinity. electron).
 The wave character of particles
De Broglie’s Hypothesis: Matter Waves
• In 1924 de Broglie wave particle duality is not restricted to radiation, but must be universal:
• all material particles possess a dual wave-particle behavior
• each material particle of momentum p behaves as a group of waves whose wavelength λ and
wave vector k are governed by the speed and mass of the particle.
• Louis de Broglie suggested that any particle, not only photons, travelling with a linear
momentum p should have a wavelength given by the de Broglie relation:
λ=

An illustration of the de Broglie relation between momentum

and wavelength. The wave is associated with a particle. A
particle with high momentum has a wavefunction with a short
wavelength, and vice versa.
 Davisson Germer Experiment
• The crucial experiment was performed by the American physicists Clinton
Davisson and Lester Germer, who observed the diffraction of electrons by a
crystal
• The Davisson–Germer experiment, shows clearly that particles have wave-like
properties, and the diffraction of neutrons is a well-established technique for
investigating the structures and dynamics of condensed phases
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The scattering of an electron beam from a nickel

crystal shows a variation of intensity characteristic of a
diffraction experiment in which waves interfere
constructively and destructively in different directions
 The dynamics of microscopic systems
• A wavefunction (, ψ (psi). is a mathematical function obtained be solving the
Schrödinger equation and which contains all the dynamical information about a
system.
• The time-independent Schrödinger equation in one dimension:

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• V(x) is the potential energy of the particle at the point x. inextricably inextricable and needs to be
expressed in more words

• ħ (which is read h-cross or h-bar) is a convenient modification of Planck’s

constant:
• ħ = = 1.054 57 × 10−34 J s
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needs to be expressed in more words; but please refine the essence of your thought as much
as possible, otherwise it is easy to cause
The Born interpretation of the wavefunction

• A principal tenet of quantum mechanics is that the wavefunction contains all the dynamical
information about the system it describes
• The interpretation of the wavefunction in terms of the location of the particle is based on a
suggestion made by Max Born.
• The Born interpretation of the wavefunction 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 itself is called the probability amplitude

The wavefunction ψ is a probability amplitude in the sense

that its square modulus (ψ*ψ or |ψ|2) is a probability density.
The probability of finding a particle in the region dx located
at x is proportional to |ψ|2 dx. We represent the probability
density by the density of shading in the superimposed band.
The Born interpretation of the
wavefunction in three-dimensional space
implies that the probability of finding the The sign of a wavefunction has no direct
particle in the volume element dτ = physical significance: the positive and
dxdydz at some location r is proportional negative regions of this wavefunction both
to the product of dτ and the value of |ψ| 2 correspond to the same probability
at that location. distribution (as given by the square modulus
of ψ and depicted by the density of shading).
Quantization Normalization
• Quantization is the confinement of a dynamical • A mathematical feature of the Schrödinger equation
observable to discrete values. is that, if ψ is a solution, then so is Nψ, where N is
any constant.
• This freedom to vary the wavefunction by a
constant factor means that it is always possible to
find a normalization constant, N, such that the
proportionality of the Born interpretation becomes
an equality.

The wavefunction must satisfy stringent conditions

for it to be acceptable.
(a) Unacceptable because it is not continuous; (b)
unacceptable because its slope is discontinuous;
(c) unacceptable because it is not single-valued;
(d) unacceptable because it is infinite over a finite
region.
 Quantum mechanical principles

• An operator is something that carries out a mathematical operation on a function. The position
and momentum operators are ẋ=x × and ῤx = (ħ/i)d/dx, respectively.
• The hamiltonian operator is the operator for the total energy of a system, Ḣψ = Eψ and is the
sum of the operators for kinetic energy and potential energy.
• An eigenvalue equation is an equation of the form Ὧψ = ωψ. The eigenvalue is the constant
ω in the eigenvalue equation; the eigenfunction is the function ψ in the eigenvalue equation.
• The expectation value of an operator is _x0001_Ω = ∫ψ*Ὧψdτ.
• An hermitian operator is one for which ∫ψi*Ὧψjdx =(∫ψj*Ὧψidx)*. The eigenvalues of hermitian
\
operators are real and correspond to observables, measurable properties of a system. The
eigenfunctions of hermitian operations are orthogonal, meaning that ∫ψi*ψj dτ = 0.
• Two operators commute when [Ὧ1,Ὧ2] = Ὧ1Ὧ2 − Ὧ2Ὧ1 = 0.
• Complementary observables are observables corresponding to non-commuting operators.
• An acceptable wavefunction must be continuous, have a continuous first derivative, be single-
valued, and be square-integrable
 Heisenberg's Uncertainty Principle
• Classical physics is thus completely deterministic Δx.Δpx ≥ ћ /2
• If the x component of the momentum of a particle is measured with an uncertainty Δ px,
then its x position cannot, at the same time, be measured more accurately than Δx= ћ /
(Δpx)
• Energy and time form a pair of complementary variable ΔE.Δt ≥ ћ /2
• Two measurements of the energy of a system and if these measurements are separated
by a time interval Δt , the measured energies will differ by an amount ΔE which can in no
way be smaller than ћ /( Δt)
• The general form of the Heisenberg uncertainty principle is ∆Ω1∆Ω2 ≥ |[Ὧ1, Ὧ2]|.

The wavefunction for a particle with an ill-defined location can be regarded as

the superposition of several wavefunctions of definite wavelength that interfere
constructively in one place but destructively elsewhere. As more waves are used
in the superposition (as givenby the numbers attached to the curves), the
location becomes more precise at the expense of uncertainty in the particle’s
momentum. An infinite number of waves is needed to construct the wavefunction
of a perfectly localized particle.
Thank You