Module 3 – Elementary Quantum Mechanics

(Wave Function &

Schrödinger’s Wave Equation)
Home Work Problem
An electron and a proton have the same velocity. Compare the wavelengths
& phase and group velocities of their de Broglie waves

de Broglie Wavelength ℎ
ℎ ℎ ℎ λ𝑒 𝑚 𝑣
λ= λ𝑒 = λ𝑝 = = 𝑒൙ℎ
𝑚𝑣 𝑚 𝑒𝑣 𝑚𝑝𝑣 λ𝑝
𝑚𝑝𝑣
λ𝑒 𝑚𝑝 λ𝑒 1.67 × 10−27 kg
= = = 1833 λ𝑒 = 1833 λ𝑝
λ𝑝 𝑚𝑒 λ𝑝 9.11 × 10 −31 kg
Phase Velocity
𝑐2 Since electron and proton 𝒗𝒑 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧 = 𝒗𝒑(𝐩𝐫𝐨𝐭𝐨𝐧)
𝑣𝑝 = have the same velocity
𝑣
Group Velocity

Since electron and proton 𝒗𝒈 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐧 = 𝒗𝒈𝐩𝐫𝐨𝐭𝐨𝐧)

𝑣𝑔 = 𝑣 have the same velocity
 Wave function

If there is a wave associated with a particle, then there must be a

function to represent it.
This function is called as a wave function

A variable quantity which characterizes de Broglie waves is known

as wave function

It is represented by Greek symbol ψ (psi), which consists of real

and imaginary parts

Ψ = A + iB
 Types of Waves

Transverse
Waves

Longitudinal
Waves

The quantity that varies periodically

Water waves → Height of the water surface

Sound waves → Pressure

Light waves → Electric and magnetic fields

Matter waves → Wave function (ψ)

 Wave Function
❑ Wave function (ψ) is a mathematical form of describing matter waves

❑ The probability of finding a moving body is described by a wave function at

the point (x, y, z) and at the time t

❑ The wave function (ψ) has no direct physical significance

Wave function (ψ) can not be interpreted in terms of an experiment – Why?

Probability that something be in a certain place at a given time must lie

between 0 (object is definitely not there) and 1 (object is definitely there)

An intermediate probability (say 0.2) means that there is a 20% chance of

finding the object

The amplitude of a wave can be negative as well as positive

A negative probability (say −0.2) is meaningless

Thus wave function (ψ) cannot be an observable quantity

 Probability Density
Probability Density |ψ|2 - The square of the absolute value of the wave function

The probability of experimentally finding the body described by the wave

function ψ at the point x, y, z at the time t is proportional to the value of |ψ|2
there at t

A large value of |ψ|2 → Strong possibility of the body’s presence

A small value of |ψ|2 → Slight possibility of the body’s presence

❑ An experiment is performed to detect electrons

An electron is either found at certain x and t or not

There is no such thing as 20% of an electron

0.2 But it is possible that there is 20% of chance

that electron be found at that x and t
A
This is specified by |ψ|2
 Physical Significances of a Wave Function
1. The wave function associated with a moving particle is not a observable
quantity and does not have any direct physical meaning (It is a complex
quantity)
2. The wave function relates the particle and wave nature statistically
3. The square of the wave function (determined by multiplying the wave function
by its complex conjugate) is a real quantity ψ 2 = ψ × ψ∗

4. │ψ │2 is the measure of the probability of finding the particle at a particular

position. It cannot predict the exact location of the particle
5. The probability values lies between 0 and 1
6. If the particle is certainly present means P = 1 and if the particle is not present
means, P = 0
7. If P = 0.4 indicates that there is a 40% chance for the presence of the particle
 Schrödinger’s Wave Equation
The behavior of sub-atomic particles (electrons) can’t be explained by
classical mechanics based on Newton’s law of motion

In 1926, Austrian physicist Erwin Schrödinger thought that if electrons

behave as waves, then it should be possible to describe them using a
wave equation

This equation (Schrödinger’s Wave equation) is the fundamental

equation of physics for describing quantum-mechanical behavior
 Schrödinger's Wave Equations

There are two forms of Schrödinger's wave equations

1. Time independent wave equation

2. Time dependent wave equation

The equation is based on three considerations

❖ Classical plane wave equation

❖ de-Broglie’s Hypothesis of matter-wave
❖ Conservation of Energy.
 Schrödinger's Wave Equations
Schrödinger derived the equations by incorporating two assumptions

Assumption – 1 2mE = 2mV + p2

E = P.E + K.E.
p2 = 2mE − 2mV
1
E = V + mv 2
2 p2 = 2m (E − V)
1 2 2 h
E= V+ m v p= 2m(E − V) λ=
2m p
p2
E=V+
2m
h
λ=
2mV + p2 2m(E − V)
E=
2m
 Schrödinger's Wave Equations
Assumption – 2

The wave function associated with the matter particles, with function of
time ‘t’ is

ψ = ψ0 e−iωt
ψ0 = amplitude of the wave at the point (x,y,z)

ω = 2πν is the angular frequency

ν = frequency
 Time Independent Schrödinger's Wave Equation
Consider a system of wave associated with a moving particle
Let ψ be the wave function of the particle along x, y, z coordinates at any
time ‘t’

Differential wave equation of a progressive wave with wave velocity ‘u’ in

terms of Cartesian coordinates (classical physics)

d2 ψ d2 ψ d2 ψ 1 d2 ψ
2
+ 2+ 2 = 2 2
dx dy dz u dt

The solution of this equation is

ψ = ψ0 e−iωt
 Time Independent Schrödinger's Wave Equation
ψ = ψ0 e−iωt

Differentiating this equation with respect to ‘t’ twice

dψ
= −iω ψ0 e−iωt
dt

d2 ψ −iωt
= (−iω) (−iω) ψ 0 e
dt 2

d2 ψ 2 2 −iωt
= i ω ψ 0 e
dt 2
i2 = −1
d2 ψ d2 ψ 2
= −ω 2
ψ 2
= −ω ψ
dt 2 dt
 Time Independent Schrödinger's Wave Equation

d2 ψ d2 ψ d2 ψ 1 d2 ψ d2 ψ 2ψ
2
+ 2+ 2 = 2 2 = −ω 𝜔 = 2𝜋𝜈 u = νλ
dx dy dz u dt dt 2

d2 ψ d2 ψ d2 ψ 1 d2 ψ d2 ψ d2 ψ 4π2 ν2
(−ω2 ψ) + 2+ 2 =− 2 2 ψ
+ + = 2 ν λ
dx 2 dy 2 dz 2 u2 dx dy dz

d2 ψ d2 ψ d2 ψ 1 2ψ
+ 2+ 2 = − 2πν 2ψ 2ψ 2ψ 2
dx 2 dy dz u2 d d d 4π
2
+ 2+ 2 =− 2 ψ
dx dy dz λ
d2 ψ d2 ψ d2 ψ 4π2 ν2
2
+ 2 + 2 =− 2 ψ
dx dy dz u
 Time Independent Schrödinger's Wave Equation

d2 ψ d2 ψ d2 ψ 4π2 h 1 2𝑚(𝐸 − 𝑉)
+ + =− 2 ψ λ= =
2m(E − V) 𝜆2 ℎ2
dx 2 dy 2 dz 2 λ

d2 ψ d2 ψ d2 ψ 2
1
2
+ 2 + 2 = −4π 2 ψ
dx dy dz λ

d2 ψ d 2 ψ d 2 ψ 2 2m(E − V)
2
+ 2
+ 2
= −4π ψ
dx dy dz h2

d2 ψ d2 ψ d2 ψ 4π2
2
+ 2 + 2 = − 2 2m(E − V) ψ
dx dy dz h
 Time Independent Schrödinger's Wave Equation
d2 ψ d2 ψ d2 ψ 4π2
2
+ 2 + 2 = − 2 2m(E − V) ψ
dx dy dz h

d2 d2 d2 2 , where ∇ is Laplacian operator

+ + = ∇
dx 2 dy 2 dz 2

4π 2
∇2 ψ = − 2 2m(E − V) ψ
h
2 8π2
8π
∇2 ψ = − 2 m(E − V) ψ ∇2 ψ = − 2 2 m(E − V) ψ
h ℏ 4π
Reduced Planck′s constant
h 2m
ℏ= → h = ℏ2π ∇2 ψ = − 2 (E − V) ψ
2π ℏ
Time Independent Schrödinger's Wave Equation

2m 2
8π
2
∇ ψ = − 2 (E − V) ψ ∇2 ψ = − 2 m(E − V) ψ
ℏ h

2
2m 8π
2
∇ ψ + 2 (E − V) ψ = 0 ∇2 ψ + 2 m(E − V) ψ = 0
ℏ h

(Schrödinger time independent wave equations)

 Significance of Schrödinger's Wave Equation
Schrodinger wave equation is a mathematical expression describing the
energy and position of the electron in space and time, taking into account the
matter wave nature of the electron inside an atom

Schrodinger equation gives us a detailed account of the form of the wave

functions or probability waves that control the motion of some smaller
particles

The equation also describes how these waves are influenced by external
factors

The equation makes use of the energy conservation concept that offers details
about the behavior of an electron that is attached to the nucleus

Besides, by calculating the Schrödinger equation we obtain Ψ and Ψ2, which

helps us determine the quantum numbers as well as the orientations and the
shape of orbitals where electrons are found in a molecule or an atom.