Chapter-Three

Wave properties of Particles

Wave Properties of Particles
“A moving body behaves in certain ways as though it has a wave nature.”
• A moving material particles behave as waves with a wavelength given by the De
Broglie wavelength. This is called the matter waves.
ℎ ℎ
𝜆= =
𝑃 𝑚𝑣
Where, m is relativistic mass for high speed particle & v is the velocity of a particle.
Example 1
Calculate the wavelength associated with a cricket ball of mass 0.2 kg moving with a
speed of 30 m/s.
𝑃 = 𝑚𝑣 = 0.2 𝑘𝑔 × 30 𝑚Τ𝑠 = 6 𝑘𝑔 𝑚Τ𝑠
ℎ 6.626×10−34 𝐽.𝑠
𝜆= = = 1.1043 × 10−34 𝑚
𝑃 6 𝑘𝑔𝑚Τ𝑠
What about for an electron having a speed of 107 m/s?
Ans: 7.27333 x 10-11 m = 0.727333 Å (Note: the radius of H atom is ≈ 0.53 Å)
• Therefore, the wave character of moving electrons is the key to understanding atomic
Therefore, even if moving ordinary objects behave in certain ways as waves, the
wave property parameters (quantities) are not conspicuous/noticeable.
For non-relativistic particles having mass m and moving with a velocity v and kinetic
energy KE = mv2/2 = P2/2m, the de Broglie wavelength is
ℎ ℎ ℎ
𝜆= = =
𝑃 𝑚𝑣 2𝑚𝐾𝐸
For high energy particles, 𝐸 2 = 𝑝2 𝑐 2 + 𝑚0 2 𝑐 4 , having kinetic energy 𝐾𝐸 = 𝐸 − 𝑚0 𝑐 2 ,
the momentum is 𝑝𝑐 = 𝐾𝐸 𝐾𝐸 + 2𝑚0 𝑐 2 and hence the de Broglie wavelength is,
ℎ ℎ ℎ𝑐
𝜆= = 𝑚𝒗 =
𝑃 𝐾𝐸 𝐾𝐸 + 2𝑚0 𝑐 2
1 − 𝑣 2 Τ𝑐 2
• Note that in certain situations a moving body resembles a wave and in others it
resembles a particle. Which set of properties is most conspicuous depends on how its
de Broglie wavelength compares with its dimensions and the dimensions of whatever it
interacts with.
Electron Diffraction – Davisson – Germer Experiment (1927)
• Proofs (confirms) the wave nature of electrons
• Davisson and Germer experimentally observed that electrons were diffracted, much
like x rays, in nickel crystals.
• Crystals act as a three-dimensional diffraction grating. The spacing b/n atoms in a
crystal is very small that it can behave like an aperture.

An electron beam is scattered from a crystal. The scattered

beam shows a diffraction pattern expected for the crystal
Spacing since diffraction and interference pattern is wave property.
Only the surface layer of atoms is considered because low-energy electrons, unlike x-rays, do not
penetrate deeply into the crystal; constructive interference occurs when the path length difference
between two adjacent rays is an integral number of wavelengths or
𝑑 sin 𝜙 = 𝑛𝜆

Al Powder
either x-ray or electrons

George Thomson Experiment X-ray pattern electron pattern

• The electron wavelength was adjusted to the same value as the x-ray by varying the voltage.
So that the diffraction pattern for x-rays and electrons are very similar.
Consequence of Wave nature of matter (electron)
1. De Broglie’s Explanation of Quantization in the Bohr Model
The fundamental postulates introduced by Bohr to explain the hydrogen atom was the notion
that the orbital angular momentum of the electron on a stationary state was quantized to
multiples of the Planck constant ħ (h/2π). This postulate can easily be shown to be consistent
with the introduction of the de Broglie wavelength, if we assume that a stationary state can
only be achieved when conditions necessary to obtain a standing matter wave are met.
𝑚𝑒 𝑣𝑟 = 𝑛ℏ 𝑤ℎ𝑒𝑟𝑒 ℏ = ℎΤ2𝜋
The allowed Bohr orbits arise because the electron matter waves will form standing waves by
interfering constructively when an integral number of wavelengths exactly fits into the
circumference of a circular orbit.
2𝜋𝑟 = 𝑛𝜆 ⟹ 𝑚𝑒 𝑣𝑟 = 𝑛ℏ
2. Invention of electron microscope
In order to create an image using optical microscope, we need light rays
(waves) that used to transfer the information of the object to be observed.
Analogously, the wave nature of moving electrons is the basis for the invention
of electron microscope.
Example: 54 eV electrons are scattered off of a surface with a strong first
maximum at an angle of 50o with respect the incoming beam of electrons. If
the spacing between the atomic planes is 0.091 nm, what is the wavelength of
the electrons from diffraction theory? What is the de Broglie wavelength of the
electrons?
Matter Wave – Waves of probability
E.g.,
Type of wave Periodically varying quantity
Water Height of water surface
Sound Density or pressure of material it propagates
Light (EM radiation) Electric & Magnetic Field
Matter ?
• The quantity whose variations make up matter waves is called the wave function,
symbol ψ (the Greek letter psi).
• Particles are really "there" and the "wave" associated with a particle isn’t the particle
"spread out." We know this because collisions seem to be instantaneous.
• Einstein though the intensity of a light wave at a given point is a measure of the
number of photons that arrive at the point. In other word, the wave function for the
electromagnetic field determines the probability of finding a photon.
• The wave function of a matter wave is not something we can see, sense or measure. It
has no direct physical significance.
• Ψ is the solution to Schrödinger's equation.
• ψ is, in general, complex. It cannot be directly measured. The time and/or space
average of ψ is zero. (That shouldn't bother you--the time/space average of a sine wave
is zero but you measured sine waves.
• In general, ψ is a function of position (x, y, z) and time.
• The wave function
Ԧҧ 𝑡 = 𝐶 𝑟,
𝜓 𝑟, Ԧ 𝑡 + 𝑖𝐷 𝑟, Ԧ
Ԧ 𝑡 = 𝐴𝑒 𝑖 𝑘𝑟−𝜔𝑡 𝑤ℎ𝑒𝑟𝑒 𝑟Ԧ 𝑖𝑠 𝑎 𝑐𝑜𝑜𝑟𝑑𝑖𝑛𝑎𝑡𝑒 𝑠𝑦𝑠𝑡𝑒𝑚 𝑜𝑓 𝑥, 𝑦, 𝑧
is the complex valued function describing the matter wave.
• The value of the wave function associated with a moving body (of matter wave) at the
particular point x, y, z in space at the time t is related to the likelihood (probability) of
finding the body there at the time.
“The probability of finding the object described by at the position (x, y, z) at time t
is proportional to the value of ψψ* (│ψ│2) there”.
• The quantity ψψ* = │ψ│2 represents the probability per unit volume (probability
density) of finding the particle at a time t in a small volume of space centered on (x, y,
z).
𝑝 𝑥 = 𝜓 𝑥 2 = 𝜓 𝑥 ∗𝜓 𝑥 ← 𝑝𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 𝑑𝑒𝑛𝑠𝑖𝑡𝑦
• The square of wave function determines the likelihood (or probability) of finding a
particle at a particular position in space at a given time.
𝑥2 𝑥2
2
𝕡 = න 𝑝 𝑥 𝑑𝑥 = න 𝜓 𝑥 𝑑𝑥 ← 𝑝𝑟𝑜𝑏𝑎𝑏𝑖𝑙𝑖𝑡𝑦 𝑜𝑓 𝑓𝑖𝑛𝑑𝑖𝑛𝑔
𝑥1 𝑥1
• Normalization: Since the particle has to be found somewhere, the sum of all the
probabilities (total probability) along the x axis has to be one:
∞ ∞
න 𝑝 𝑥 𝑑𝑥 = න 𝜓 𝑥 2 𝑑𝑥 =1
−∞ −∞
• A wave function that satisfies this condition is said to be normalized.
• A large value of │ψ│2 means the strong possibility of the body’s presence, while a
small value of │ψ│2 means the slight possibility of its presence.
Wave Functions and Wave Packets
Consider a one-dimensional simple harmonic motion wave propagating in the positive x
direction with a phase speed vp. Note that vp is the speed of a point of constant phase on
the wave, such as a wave crest or trough. This traveling wave with wavelength λ,
frequency f, and amplitude A may be described by
2𝜋
𝑦 = 𝐴 cos 𝑥 − 2𝜋𝑓𝑡 = 𝐴 cos 𝑘𝑥 − 𝜔𝑡
𝜆
𝜔
Where, the phase velocity 𝑣𝑝 = 𝜆𝑓 =
𝑘
ω = 2πf rad/s is angular frequency – the number of radians corresponding to a wave
train of 1s long.
k = 2π/λ rad/m is wave number – the number of radians corresponding to a wave
train of 1m long.
• The matter wave representing a moving particle must reflect the fact that the
particle has a large probability of being found in a small region of space only at a
specific time. This means that a traveling sinusoidal matter wave of infinite
extent and constant amplitude resembling above equation cannot properly
represent a localized moving particle.

• What is needed is a pulse, or “wave group,” of limited spatial extent. Such a

pulse can be formed by adding sinusoidal waves with different wavelengths. The
resulting wave group can then be shown to move with a speed vg (the group
speed) identical to the classical particle speed. This argument is shown
schematically in Figure below.
• The particle that corresponds to the specified wave group may be located
anywhere within the group at a given time. Of course, the probability
density│ψ│2 is a maximum in the middle of the group since the amplitude
is maximum there, so it is most likely to be found there. Nevertheless, we
may still find the particle anywhere that │ψ│2 is not actually 0.
• Actually, all observed waves are limited to definite regions of space and are called
pulses, wave groups, or wave packets in the case of matter waves.
• A wave group consists of a superposition of waves with different wavelengths and
velocity, with the amplitude and phase of each component wave adjusted so that the
waves interfere constructively over a small region of space and outside of this region
the combination of waves produces a net amplitude that approaches zero rapidly as a
result of destructive interference.
• The most familiar physical example in which wave groups arise is the phenomenon
of beats. Beats occur when two sound waves of slightly different wavelength (and
hence different frequency) are combined.
• The resultant sound wave has a frequency equal to the average of the two combining
waves and an amplitude that fluctuates, or “beats,” at a rate given by the difference
of the two original frequencies.
Let us now form the superposition of two waves of equal amplitude both
traveling in the positive x direction but with slightly different wavelengths,
frequencies, and phase velocities.
𝑦1 = 𝐴 cos 𝑘1 𝑥 − 𝜔1 𝑡 & 𝑦2 = 𝐴 cos 𝑘2 𝑥 − 𝜔2 𝑡
The resultant amplitude y is given by
𝑦 = 𝑦1 + 𝑦2 = 𝐴 cos 𝑘1 𝑥 − 𝜔1 𝑡 + 𝐴 cos 𝑘2 𝑥 − 𝜔2 𝑡

Using the trigonometric identity

1 1
cos 𝛼 + cos 𝛽 = 2 cos 𝛼 + 𝛽 cos 𝛼 − 𝛽 & cos −𝜃 = cos 𝜃
2 2
We get
1 1
𝑦 = 2𝐴 cos 𝑘2 − 𝑘1 𝑥 − 𝜔2 − 𝜔1 𝑡 cos 𝑘1 + 𝑘2 𝑥 − 𝜔1 + 𝜔2 𝑡
2 2
• For the case of two waves with slightly different values of k and ω, we see
that ∆k = k2 – k1 and ∆ω = ω2 – ω1 are small, but (k1 + k2) and (ω1 + ω2) are
large.
Then, the above equation can be written as:
∆𝑘 ∆𝜔 𝑘1 + 𝑘2 𝜔1 + 𝜔2
𝑦 = 2𝐴 cos 𝑥− 𝑡 cos 𝑥− 𝑡
2 2 2 2
This superposition of two waves is shown in Figure below.
The wave function y may be interpreted as a broad sinusoidal envelope
∆𝑘 ∆𝜔
2𝐴 cos 𝑥− 𝑡
2 2
limiting or modulating a high-frequency wave within the envelope
𝑘1 + 𝑘2 𝜔1 + 𝜔2
cos 𝑥− 𝑡
2 2
• The envelope and the wave within the envelope move at different speeds. The velocity
for the wave within the envelope is a phase speed,
𝜔1 + 𝜔2 Τ2 𝜔1 𝜔2
𝑣𝑝 = ≈ = 𝑣1 ≈ = 𝑣2
𝑘1 + 𝑘2 Τ2 𝑘1 𝑘2
• The envelope or group velocity is given by
𝜔2 − 𝜔1 Τ2 ∆𝜔
𝑣𝑔 = =
𝑘2 − 𝑘1 Τ2 ∆𝑘
• The general characteristic of wave groups for waves of any type is both a limited
duration in time, ∆t, and a limited extent in space, ∆x.
• The smaller the spatial width of the pulse, ∆x, the larger the range of wavelengths
or wavenumbers, ∆k, needed to form the pulse.
• ∆𝑥∆𝑘 ≈ 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• If the time duration, ∆t, of the pulse is small, we require a wide spread of
frequencies, ∆ω, to form the group. That is,
• ∆𝑡∆𝜔 ≈ 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• Therefore, both ∆x and ∆k or ∆t and ∆ω cannot become arbitrarily small, but as
one decreases the other must increase. Therefore, the above equations represent
“uncertainty relations,” or “reciprocity relations,” for pulses of any kind.
• The precise value of the number on the righthand side of the above equations
depends on the functional form (shape) f(x) of the wave group as well as on the
specific definition of ∆x and ∆k or ∆t and ∆ω. A different choice of f(x) or a
different rule for defining ∆x and ∆k (or both) will give a slightly different
number.
• In the general case, many waves having a continuous distribution of wavelengths
must be added to form a wave packet that is finite over a limited range and really
zero everywhere else. In this case, the equation for the group velocity, vg becomes

𝑑𝜔 𝑑𝐸
• 𝑣𝑔 = ቚ =
𝑑𝑘 𝑘0 𝑑𝑝

• Where k0 is the central wavenumber of the many waves present.

• Since ω = kvp, the relationship between the group velocity and the phase
velocity of the composite waves is easily obtained as,

𝑑𝜔 𝑑𝑣𝑝
𝑣𝑔 = ቤ = 𝑣𝑝 ቚ + 𝑘 ቤ
𝑑𝑘 𝑘 𝑘0 𝑑𝑘 𝑘
0 0

where vp is the phase velocity and is, in general, a function of k or λ.

• For waves propagating through the materials medium in which the phase
velocity varies with wavelength are said to exhibit dispersion. In a dispersive
medium the group velocity can be less than or greater than the phase velocity,
depending on the sign of dvp/dk, as shown by the above equation. E.g.,
electromagnetic waves traveling through the glass
• Media in which the phase velocity does not vary with wavelength (such as
vacuum for electromagnetic waves) are termed nondispersive. In a nondispersive
medium where all waves have the same velocity, the group velocity is equal to the
phase velocity.
• Read the sub-topic Matter Wave Packets in text book – Serway at page 169.
• The individual de Broglie waves representing a particle of mass m show
dispersion even in empty space and always travel at a speed that is greater than or

𝑚𝑐 2 𝑐2 𝐸
at least equal to the speed of light c (𝑣𝑝 = 𝑐 1 + 𝑜𝑟 𝑣𝑝 = or 𝑣𝑝 = ).
ℏ𝑘 𝑣 𝑃

• The envelope or group velocity vg of the matter wave packet is the same as the
particle speed (vg = v).
Fourier Integrals
• To form a true pulse that is zero everywhere outside of a finite spatial range ∆x requires
adding together an infinite number of harmonic waves with continuously varying
wavelengths and amplitudes. This addition can be done with a Fourier integral, which is
defined as follows: +∞
1
𝜓 𝑥 = න 𝑔 𝑘 𝑒 𝑖𝑘𝑥 𝑑𝑘
2𝜋 −∞
• Here ψ(x) is a spatially localized wave group, g (k) gives the amount or amplitude of the
wave with wavenumber k = (2π/λ) to be added to form ψ (x), and eikx = cos kx + i sin kx is
Euler’s compact expression for a harmonic wave. The amplitude distribution function g
(k) can be obtained if ψ (x) is known by using
+∞
the symmetric formula
1
𝑔 𝑘 = න 𝜓 𝑥 𝑒 −𝑖𝑘𝑥 𝑑𝑘
2𝜋 −∞
• The above equations apply to the case of a spatial pulse at fixed time, but it is important to
note that they are mathematically identical to the case of a time pulse passing a fixed
position.
Thus, the representation of the moving wave +∞ packet becomes
1
𝜓 𝑥, 𝑡 = න 𝑔 𝑘 𝑒 𝑖 𝑘𝑥−𝜔𝑡 𝑑𝑘
2𝜋 −∞
Here ω = ω (k), that is, ω is a function of k and therefore depends on the type of wave and the
medium traversed.
• The minimum value of the product ∆x ∆k occurs when the envelope of the group has
the familiar bell shape of a Gaussian function. In this case the Fourier transform
happens to be a Gaussian function also. If x and k are taken as the standard deviations
of the respective functions f(x) and a(k), then this minimum value is ∆x ∆k = ½.
Because wave groups in general do not have Gaussian forms, it is more realistic to
express the relationship between ∆x and ∆k as
1
∆𝑥∆𝑘 ≥
2

Figure: The wave functions and Fourier transforms for (a) a pulse, (b) a wave
group, (c) a wave train, and (d) a Gaussian distribution.
The Heisenberg Uncertainty Principle
• Heisenberg introduced the notion that it is impossible to determine simultaneously
with unlimited precision the position and momentum of a particle.
❖ If a measurement of position is made with precision ∆x and a simultaneous
measurement of momentum in the x direction is made with precision ∆px, then the
product of the two uncertainties can never be smaller than ħ/2. That is,
ℏ
∆𝑃𝑥 ∆𝑥 ≥
2
ℎ
Where ℏ =
2𝜋
• The uncertainties ∆px and ∆x does not arise from imperfections in practical measuring
instruments. Rather, they arise from the need to use a large range of wavenumbers, ∆k,
to represent a matter wave packet localized in a small region, ∆x. Therefore, it is
impossible to know both the exact position and exact momentum of an object at the
same time.
• The narrower a moving particles wave group, the more precisely a particle’s
position can be specified. However, the wavelength of the waves in a narrow
packet is not well defined; there are a greater range of wavelength to measure λ
accurately. This means that since λ = h/p, the particle’s momentum p is not a
precise quantity, we will find a broad range of values.
• On the other hand, a wide wave group has a clearly defined wavelength. The
momentum that corresponds to this wavelength is therefore a precise quantity, and
a series of measurements will give a narrow range of values. But where is the
particle located? The width of the group is now too great for us to be able to say
exactly where the particle is at a given time.
• Another important uncertainty relation involves the uncertainty in energy of a wave

packet, ∆E, and the time, ∆t, taken to measure that energy. Starting with ∆ω∆t = ½ as

the minimum form of the time–frequency uncertainty principle, and using the de

Broglie relation for the connection between the matter wave energy and frequency, E =

ħω, we immediately find the energy–time uncertainty principle

ℏ
∆𝐸∆𝑡 ≥
2

• The precision with which we can know the energy of some system is limited by the

time available for measuring the energy.

Particle in a Box
• The assumptions for a particle that bounces back and forth between the walls of a box:
➢ A particle is trapped in a box of length L.
➢ The velocity of a particle is sufficiently small so that we can ignore relativistic
considerations.
➢ The walls of the box are infinitely hard, so the particle does not lose energy each
time it strikes a wall.
• The matter wave of a particle trapped in a box is act as a standing wave. The wave
variable or the wave function ψ for the moving particle must be 0 at the walls, since
the particle and its associated wave stops there.
• The possible de Broglie wavelengths of the particle in the box therefore are determined
by the width L of the box, as shown in Figure below. The longest wavelength is
specified by λ = 2L, the next by λ = L, then λ = 2L/3, and so forth. The general formula
for the permitted wavelengths is
2𝐿
𝜆𝑛 = 𝑤ℎ𝑒𝑟𝑒 𝑛 = 1, 2, 3, …
𝑛
• Because mv = h/λ, the restrictions on de Broglie wavelength λ imposed by the width of
the box are equivalent to limits on the momentum of the particle and, in turn, to limits
on its kinetic energy. The kinetic energy of a particle of momentum mv is
1 𝑚𝑣 2 ℎ 2
𝐾𝐸 = 𝑚𝑣 2 = =
2 2𝑚 2𝑚𝜆2
• Since the permitted wavelengths are λn = 2L/n, and so, the particle has no potential
energy in this model, the only energies it can have are
𝑛2 ℎ2
𝐸𝑛 = 2
𝑤ℎ𝑒𝑟𝑒 𝑛 = 1, 2, 3, …
8𝑚𝐿
• Each permitted energy is called an energy level, and the integer n that specifies an
energy level En is called its quantum number.
• The general conclusions applied to any particle confined to a certain region of space
(even if the region does not have a well-defined boundary) is
1) A trapped particle cannot have an arbitrary energy, as a free particle can. The fact of its
confinement leads to restrictions on its wave function that allow the particle to have only
certain specific energies and no others. Exactly what these energies are depends on the mass
of the particle and on the details of how it is trapped.
2) A trapped particle cannot have zero energy. Since the de Broglie wavelength of the particle
is λ = h/mv, a speed of v = 0 means an infinite wavelength. But there is no way to reconcile
an infinite wavelength with a trapped particle, so such a particle must have at least some
kinetic energy. The exclusion of E = 0 for a trapped particle, like the limitation of E to a set
of discrete values, is a result with no counterpart in classical physics, where all non-negative
energies, including zero, are allowed.
3) Because Planck’s constant is so small—only 6.626 x 10-34 J.s—quantization of energy is
conspicuous only when m and L are also small. This is why we are not aware of energy
quantization in our own experience.
Exercise

1. Calculate the de Broglie wavelength of a proton which are accelerated by a

potential difference of 4000 V. When we observe the scattered beam of proton, the
second interference maxima is found to be at angle of 300 from the axis of incident
beam. Determine the interatomic separation distance between successive
neighboring target atoms? (Hint: the mass of a proton = 1.007825 amu & 1 amu =
1.660 538 73 X 10-27 kg )
Calculate the de Broglie wavelength of a typical helium atom on a hot summer day
(37oC ). when we scatter this beam of He through a single crystal target, the principal
interference maxima is shown to happen at angle of 450 from the axis of the beam.
Determine the interatomic separation distance between successive neighboring target
atoms? (Hint: the mass of a He atom = 4.002603 amu & 1 amu = 1.660 538 73 X 10-27
kg )