MODULE 2

THE WAVE FUNCTION

Course code; PY310
Course instructor, Ms. Andongolile, T
Department of Physics & Mathematics
Probability and uncertainty
• Unlike Newtonian particles, photons, cannot be treated as a
point object.
• This is because there are fundamental limitations on the
precision with which we can simultaneously determine the
position and momentum of a photon.
• Many aspects of a photon’s behavior can be stated only in
terms of probabilities
Consider the single-slit diffraction of light below
• Suppose the wavelength λ is much less than the slit width
a, then most (85%) of the photons go into the central
maximum of the diffraction pattern, and the remainder go
into other parts of the pattern.
• If θ1 is the angle between the central maximum and the
first minimum, then for m = 1,
λ
sin 𝜃1 = 𝑎
For λ << a,
λ
𝜃1 =
𝑎
From figure above
𝑝𝑦
tan 𝜃1 =
𝑝𝑥
For small angle tan 𝜃1 = 𝜃1
Py = 𝜃1px
λ
Py = px
𝑎
For the 85% of the photons that strike the detector within the
central maximum (that is, at angles between -λ/a and +λ/a), the
y-component of momentum is spread out over a range from
λ λ
+ px to - px
𝑎 𝑎
• There is an uncertainty Δpy in the y-component of
momentum at least as great as pxλ/a.
That is
λ
∆Py ≥ px
𝑎
• The narrower the slit width a, the broader is the diffraction
pattern Also,

The slit width a represents an uncertainty in the y-component

of the position of a photon as it passes through the slit
• Heisenberg uncertainty principle has a root in wave
aspect photon
WAVE FUNCTION
• In classical wave motion, transverse waves on a string are
described by specifying the position of each point in the
string at each instant of time by means of a wave
function y(x, t) that represents the displacement from
equilibrium, at time t, of a point on the string at a
distance x from the origin
• The velocity and acceleration of any point on the string
at any time can be found
• Sound wave and EMT waves are also represented in
similar way
• Thus, it’s natural to use a wave function as the central element
in quantum mechanics
• The symbol for this wave function is the Greek letter psi, Ψ
• Just as the wave function y(x, t) for mechanical waves on a
string provides a complete description of the motion,
• So the wave function Ψ(x, y, z, t) for a particle contains all the
information that can be known about the particle.
Wave function in One Dimension
Consider one-dimensional motion, in which a particle of mass
m moves parallel to the x-axis and the wave function Ψ
depends on the coordinate x and the time t only.
• Any wave function y(x, t) that describes a wave on a string
must satisfy the wave equation
𝜕2𝑦(𝑥,𝑡) 1 𝜕2
𝑦(𝑥,𝑡)……………………………………..(1)
=v2
𝜕𝑥2 𝜕𝑡2
Consider the following wave function moving in the positive
x-direction along a string:
y(x,t)= A cos(kx -wt)+B sin(kx - wt)……………(2)
k = 2π/λ is the wave number and ω= 2πf is the angular
frequency, A and B are constant.
 𝜕𝑦(𝑥,𝑡)
=-Ak sin(kx -wt)+Bk cos(kx - wt)
𝜕𝑥
𝜕2𝑦(𝑥,𝑡) 2 cos (kx -wt) - Bk2 sin(kx -
=-Ak wt)……..(i)
𝜕𝑥2
Also
𝜕2𝑦(𝑥,𝑡)
= -Aw2 cos (kx -wt) - Bw2 sin(kx - wt)…….(ii)
𝜕𝑡2
Substitute to eqn(1)
1
-Ak2 cos (kx -wt) - Bk2 sin(kx - wt) = ( −Aw 2 cos (kx −wt) −
v2
Bw2 sin(kx − wt))
 2 𝑤2
k = 𝑣2 also w = vk
Also

This shows that Eq. (2) is a valid wave function for waves on a
string for any values of A and B
In a quantum-mechanical version of the wave equation
• We can consider a free particle, one that experiences no
force at all as it moves along the x-axis.
• Then the energy of the free particle is equal to its kinetic
energy, which we can express in terms of its momentum p:
2 2
1 𝑚 𝑣 𝑝2
KE = 𝑚𝑣 =
2 =
2 2𝑚 2𝑚

ħ2𝑘2
ħω = 2𝑚 … … … … … . . (𝑐)
• By analogy, a sinusoidal wave function Ψ(x, t) represents a
free particle of mass m, momentum p = ћk, and energy E =
ћω moving in the positive x-direction
y(x,t)= A cos(kx -wt)+B sin(kx - wt)
ħ2 𝜕2Ψ(x,𝑡) ħ2 2 cos (kx -wt) - Bk2 sin(kx - wt))
- = - (-Ak
2𝑚 𝜕𝑥2 2𝑚
ħ2 𝜕2Ψ(x,𝑡) ħ2k2
- 2 =- (-Acos (kx -wt) - Bsin(kx - wt))
2𝑚 𝜕𝑥 2𝑚
ħ2k2
= Ψ(x,𝑡)
2𝑚
 ħ2 𝜕2Ψ(x,𝑡) ħ2k2
• This Equation suggests that - 2 = Ψ(x,𝑡)
2𝑚 𝜕𝑥 2𝑚
to satisfy wave eqn.(c)
• Assume the right-hand side of our quantum-
𝜕Ψ(x,𝑡)
mechanical wave equation involves ħ
𝜕𝑡
Therefore our tentative equation is as,
ħ2 𝜕2Ψ(x,𝑡) 𝜕Ψ(x,𝑡)
- 2 = Cħ ………………….3)
2𝑚 𝜕𝑥 𝜕𝑡
C as a “fudge factor” to make sure that everything turns
out right
Substituting the wave functions as discussed, We find that

ħ2k2
= ħ𝑤 therefore,
2𝑚
• Equating the coefficients, we find that,
A = -CB
B = CA
Solving simultaneously,
A = -C2A -1 = C2
C = i, B = iA
• From eqn (3),
ħ𝟐 𝝏𝟐Ψ(x,𝒕) 𝝏Ψ(x,𝒕)
- 𝟐 = iħ ……….This is the one-
𝟐𝒎 𝝏𝒙 𝝏𝒕
dimensional Schrödinger equation for a free particle,
 Solution to the wave eqn above
• The presence of the imaginary number i in Eq. above means
that the solutions to the Schrödinger equation are complex
quantities, with a real part and an imaginary part.
• The wave function becomes
y(x,t)= A cos(kx -wt)+iAsin(kx - wt)
From Euler’s formula,
• Thus, our sinusoidal free-particle wave function becomes
𝑖(𝑘𝑥−𝜔𝑡)
Ψ(x,𝑡) = A𝑒 ………………………….(d)
• As we saw earlier, Ψ(x, t) describes the distribution of a
particle in space
• In interference and diffraction, the intensity I of the radiation
at any point in a pattern is proportional to Efield2 and
probability that any individual photon will strike around the
point
• In the same way, the square of the wave function of a
particle at each point tells us about the probability of finding
the particle around that point.
• Or the square of the absolute value of the wave
function, |Ψ|2, this is because, is a complex quantity
with real and imaginary parts.
• For a particle that can move only along the x-direction,
the probability that the particle will be found at time t at
a coordinate in the range from to x+dx.
∞
i.e.
‫׬‬−∞ |Ψ(𝑥, 𝑡)|2𝑑𝑥 =1
• That is, the integral of |Ψ(x, t)|2dx over all possible
values of x must equal exactly 1, that the particle is
somewhere.
• Probability distribution function |Ψ(x, t)2= ψΨ*
Complex conjugate of eqn.(d)
Ψ*(x,t) =
Hence the probability distribution function is

This also means that the wave function can’t be normalized:

The integral of |Ψ(x, t)2 over all space is infinite for any value
of A.
Example
The wave function
𝑖(𝑘1𝑥−𝜔1𝑡) 𝑖(𝑘2𝑥−𝜔2𝑡)
Ψ(x,𝑡) = A𝑒 + A𝑒
is a superposition of two free particle wave functions of the
form given by eqn (*). Both k1 and k2 are positive.
(a) Show that this wave function satisfies the Schrödinger
equation for a free particle of mass m.
(b) Find the probability distribution function for Ψ(x, t)2.

Solution
If we substitute Ψ(x, t)2 into a one-dimensional Schrödinger
equation for a free particle
 ħ𝟐 𝝏𝟐Ψ(x,𝒕) 𝝏Ψ(x,𝒕)
- 𝟐 = iħ
𝟐𝒎 𝝏𝒙 𝝏𝒕
The left-hand side of the equation is
The right-hand side

The two sides are equal, provided that

ħ2k12 ħ2k22
= ħω1 and = ħω2
2𝑚 2𝑚
Therefore, a given function is a valid free particle wave function
(b) The complex conjugate of Ψ(x, t) is
−𝒊(𝒌𝟏𝒙−𝝎𝟏𝒕) −𝒊(𝒌𝟐𝒙−𝝎𝟐𝒕)
Ψ(x,𝒕) = A𝒆 + A𝒆
• From Euler’s equation
Wave Packets
• The discussed wave function can’t be normalized because it is not
very well localized:
• It extends from x = -ꝏ to x = +ꝏ
• To localize a wave function within a region of space of width x, we
superpose a large number of sinusoidal waves with different wave
numbers and appropriate amplitudes
• This produces a wave pulse that has a wavelength λav = 2π/kav.
• This localized pulse has aspects of both particle and wave.
• A localized wave pulse shown in figure below is called a wave
packet
• Real part of the wave function at time t
• Imaginary part of the wave function at time t
We can represent a wave packet by an expression such as

• This integral represents a superposition of a very large number

of waves, each with a different wave number k and angular
frequency ω and each with an amplitude A(k) that depends on
k.
 THE HARMONIC OSCILLATOR
• Systems that oscillate are of tremendous importance in the
physical world, from the oscillations of the eardrums in
response to a sound wave to the vibrations of the ground
caused by an earthquake.
• A microwave oven transfers energy to food by making water
molecules in the food flip back and forth
A harmonic oscillator
Is a particle with mass ‘m’ that moves along the x-axis under
the influence of a restoring force Fx = -kʹx
• Acceleration of the particle at any position is directly
proportional to the displacement from the mean position
• The constant kʹ is called the force constant
• In classical physics an electron oscillating with angular
frequency ω emits electromagnetic radiation with that same
angular frequency.
• When an excited quantum-mechanical harmonic oscillator
2 𝑘
with angular frequency ω = 𝑚 makes a transition from one
energy level to a lower level, it emits a photon with this same
angular frequency ω
• The energy of such a photon is

Thus

This is the spacing between adjacent energy levels of the

harmonic oscillator
Variation of Energy in classical oscillator
E =K E+PE
1 2
V(x)= kx
2
K.E= 12𝑚ω2 (A2-x2)
1
ET = 2𝑚ω2 A2
KE V(x)
Harmonic Oscillator in Quantum Mechanics
• The Schrödinger equation for the one-dimensional
harmonic oscillator with potential energy can be
written as follows

• To find the allowed energies E and their corresponding

solution to wave functions ψ(x) —we require the wave
functions to be symmetric about x=0 and to be
normalizable.
• These conditions ensure that the probability
density |ψ(x)| 2 must be finite when integrated over the entire
range of x from −ꝏ to +ꝏ
• The solution of this wave equation is the subject of a more
advanced course in quantum mechanics;
• The allowed energies are.
1
En = 𝑛 + ħω, n=0, 1, 2, 3………………
2
Allowed energies in harmonic oscillator
• The solution for the wave functions above that correspond
to these energies (the stationary states or states of definite
energy) are
−𝛽2𝑥2/2
Ψn(x) =Nn𝑒 Hn(βx), n= 0, 1, 2, 3, …….
𝑚𝜔
β= ħ

Nn = normalization constant, and

Hn(x) =Hermite polynomial of degree ‘n’
Generation of Hermitian polynomial
Hermitian polynomial are generated using the following
2 𝑛 2
Hn(x) = n
(-1) 𝑒 x 𝑑
𝑒 −x
𝑑xn
The first four Hermite polynomial are
H0(x) = 1
H1(x) =2x
H2(x) =4x2-2
H3(x) =8x3-12x
 CENTRAL FORCES
❖ A force that always acts on a particle or body towards
or away from a fixed point.
❖Magnitude depends upon only the distance from the
fixed-point
 Central force is given as
Ԧ 𝑟Ƹ
F= 𝑓(r)
Ԧ magnitude of force
𝑟Ƹ unit vector, 𝑓(r)
Example of central forces
i. Gravitational force
ii. Electrostatic force
iii. Magnetostatic force
 Properties of central forces
❖Central force is always conservative in nature
f(r) =-dV/dr
F(r) is the magnitude of the central force.
V(r) is time-independent potential energy.
❖It is attractive if f(r)<0 and repulsive if f(r)>0
❖The angular momentum of the particle is conserved, i.e. is
constant
❖The time rate of change in area (i.e. the areal velocity) is
constant. This is sometimes called the law of areas
 Activity
1. Find the amplitude A of oscillations for a classical oscillator
with energy equal to the energy of a quantum oscillator in the
quantum state n.
2. The HCl diatomic molecule consists of one chlorine atom and
one hydrogen atom. Because the chlorine atom is 35 times more
massive than the hydrogen atom, the vibrations of the HCl
molecule can be quite well approximated by assuming that the
Cl atom is motionless and the H atom performs harmonic
oscillations due to an elastic molecular force modeled by
Hooke’s law. The infrared vibrational spectrum measured for
hydrogen chloride has the lowest-frequency line centered at f
= 8.8 x 1013 Hz . What is the spacing between the vibrational
energies of this molecule? What is the force constant k of the
atomic bond in the HCl molecule?
Solution 1
From classical energy
1
ET = 2𝑚ω2 A2
1
En = 𝑛 + ħω,
2

2.
 Transitions Between Energy States
❖From the Schrödinger equation the energy is quantized for
bound systems
❖The existence of these energy levels is determined
experimentally by observation of the energy emitted or
absorbed when the system makes a transition from one level
to another.
❖Consider a particle with charge ‘q’ in a quantum state ‘n’
described by the wave function
Ψ(x,𝑡) = Ψn (𝑥)𝑒 −𝑖𝐸𝑛𝑡/ħ
En =energy, Ψn(x) S.E solution for some potential.
❖The probability of finding the charge in dx is
P= Ψn* Ψndx
❖an identical system with the amount of charge ‘q’ and charge
density
𝜌n= qΨn* Ψndx

❖The probability density is independent of time if the wave

function contains a single energy, so the charge density for this
state is also independent of time
❖Now systems make transitions from ‘n’ energy state to ‘m’
with the emission or absorption of radiation
Ψnm(x, t)=aΨn(x, t)+ bΨm(x, t)
Ψn(x) and Ψm(x) are real
a and b = constant
❖Probability density
Ψ*nmΨnm = a2ΨnΨ*n + b2ΨmΨ*m +ab (Ψ*nΨm+ Ψ*m Ψn)
First two terms are independent of time
Ψ*n(x,t)Ψm(x,t) = Ψ∗n𝑒 𝑖𝐸𝑛𝑡/ħ Ψm 𝑒 −𝑖𝐸𝑚𝑡/ħ …….(1)
 hf =ħωnm=En-Em
ωnm= E n −Em……Bohr frequency
ħ
Rewriting eqn 1
Ψ*n(x,t)Ψm(x,t) = Ψ*nΨm 𝑒 𝑖ωnm𝑡
Again
Ψ*m (x,t) Ψn (x,t) = Ψ∗m𝑒 𝑖𝐸𝑛𝑡/ħ Ψm𝑒 −𝑖𝐸𝑚𝑡/ħ
𝑖ωmn𝑡
= Ψ*mΨn 𝑒
Using Eurel Equation
𝑒 𝑖𝜔𝑡 + 𝑒 −𝑖𝜔𝑡 =2cos(ωnmt)
❖Rewriting the probability equation
|Ψnm(x,t)|2= a2Ψ2n + b2Ψ2m +2ab ΨnΨmcos(ωnmt)

❖Thus, the wave function consisting of a mixture of

two energy states leads to a charge distribution that
oscillates with the Bohr frequency ω
 ANGULAR MOMENTUM OPERATOR
❖According to classical mechanics angular momentum L
𝐿=𝑟 ×𝑃
In equation (7) 𝐿෠ x, 𝐿෠ y, 𝐿෠ z are the angular momentum operators
in Cartesian coordinates.
On taking the square of eqn (7) we get
𝐿෠ 2 =𝐿෠ 2x+𝐿෠ 2y+ 𝐿෠ 2z
ANGULAR MOMENTUM OPERATOR
 SPIN WAVE FUNCTION AND REPRESENTATION
❖The electron itself possesses an intrinsic angular momentum
a spin independent of orbital angular momentum
❖It is described by a spin quantum number ‘s’ can be integral
and non-integral numbers
3
❖s can take half-integer or integer values (e.g., 𝑠=0, 2, 1, ,2,…)
1
2
❖For a given 𝑠, the magnetic spin quantum number 𝑚𝑠
describes the possible projections of spin along a chosen axis
(usually 𝑧-axis):
ms = −s,−(s−1),…,s.
❖For example: For 𝑠=1/2 : 𝑚𝑠=±1/2 (two states: "spin-up"
and "spin-down").
❖For 𝑠=1: 𝑚𝑠=−1,0,+ (three states).
❖Like every angular momentum spin of an electron is a vector
with three spatial components sx, sy, sz
S= sx, sy, sz
❖In the chosen direction, the magnitude of electron spin
angular momentum is ħ/2 or -ħ/2
Spin operators, wave function and Matrices
• Intuitively, one state is spin up and other is spin down
• The wave function should correspond to the direction i.e.∅ ↑
𝑎𝑛𝑑 ∅ ↓
• Measurement of z component will be accompanied by applying
𝑠Ƹ z operator to a wave function
• We choose the wavefunction in such a way that application of
operator gives the observed value. ħ/2 and -ħ/2
i.e …………….(a)

…………….(b)
❖These can be summarized as

ms=quantum number of spin

❖We are looking for formalization which will give us eqn (a)&(b)
That can be easily done by using matrix.
Example

We are thus looking for a vector ′∅′ and matrix ‘M’ such that
M∅ yields exactly either

We shall simply give the result and then verify. We choose 𝑠Ƹ z

And the spin wave function in form of

Eqn a &b can be written as

ħ
ħ 1 0 1
M ∅ ↑= 0
= 2
2 0 −1 0
ħ 1 0 0 0
M∅ ↓= 1
= −ħ
2 0 −1 2
ħ −ħ
∴ M∅ ↑ = ∅, M∅ ↓= ∅
2 2
For normalization condition we introduce a scalar ∅’s
If we have general form of the wave as

We define scalar product

………….(2)
❖Substitute the following in eqn (2)

❖We obtain

ഥ 1= ∅
❖With ∅ ഥ ↓ and ∅ = ∅ ↑ we have

❖i.e. the wave function are mutually orthogonal

❖Also spin momentum in x any y direction

❖ To calculate 𝑠Ƹ 2 = 𝑠Ƹ 2 x+ 𝑠Ƹ 2y+ 𝑠Ƹ 2z we obtain

 ASSIGNMENT
1. Show step by step how to find the solution of the radial
equation of hydrogen
2. Show that angular momentum operators are Hermitian
operators
3. Investigate if they commute
𝐿෠ x, 𝐿Ƹ y , 𝐿෠ x, 𝐿Ƹ z , 𝐿෠ y, 𝐿zƸ , 𝐿෠ z, 𝐿Ƹ 2