Group velocity & Phase velocity

The phase velocity of a wave is the rate at which the phase of the wave propagates in space.
The group velocity of a wave is the velocity with which the overall shape of the wave’s amplitudes
— known as the modulation or envelope of the wave — propagates through space.
Suppose a wave packet if formed by combination of two waves having same amplitude ‘a’
but different angular frequencies ω and ω’ and wave numbers k & k’.
The wave equation for these two waves can be represented as:
y1 = a cos (ωt-kx)…………………..[1]
y2 = a cos (ω’t-k’x)………………….[2]
According to principle of superposition the resultant wave motion at any point x and at time t is
given by:
Y=y1+y2
Y= a [cos(ωt-kx)+ cos (ω’t-k’x)]…………………….[3]
Using identity,
(𝑐+𝑑) (𝑐−𝑑)
cos c+cos d= 2 cos 2
cos 2

So in equation 3, c= (ωt-kx) & d= (ω’t-k’x)

(ωt−kx)+(ω’t−k’x) (ωt−kx)−(ω’t−k’x)
Y= 2a cos 2
cos 2

(ω+ω’)t−(k+k’)x (ω−ω’)t−(k−k’)x
= 2a cos cos
2 2
∆ωt−∆𝑘𝑥
Y= 2a cos (ωt − kx)cos …………………………[4]
2

∆ωt−∆𝑘𝑥
Where amplitude of wave packet = 2acos 2
and phase = cos (ωt − kx)

Since phase is constant (ωt − kx)= constant

Therefor Phase velocity
𝑑𝑥 ω
vp = 𝑑𝑡 = 𝑘

For the amplitude of the wave packet to be constant

∆ωt ∆𝑘𝑥
2
− 2
= constant

Group velocity
 ∆ωt
𝑑𝑥 2 ∆ω
vg= = ∆𝑘𝑥 = ∆𝑘
𝑑𝑡
2

∆ω 𝑑ω
vg = lim = 𝑑𝑘
ω→ω’ ∆𝑘

ω
Since 𝑘 = 𝑣 p & ω = 𝑣p 𝑘

Therefore, group velocity

𝑑
𝑣𝑔 = (𝑘𝑣𝑝 )
𝑑𝑘
𝑑
=𝑣𝑝 + 𝑘 𝑑𝑘 𝑣𝑝

2𝜋 𝑑𝑣𝑝
= 𝑣𝑝 + .
𝜆 𝑑(2𝜋)
𝜆

2𝜋 𝑑𝑣𝑝
= 𝑣𝑝 + .
𝜆 𝑑 (2𝜋)
𝜆
𝑑𝑣𝑝
= 𝑣𝑝 − 𝜆
𝑑𝜆

Heisenberg’s uncertainty principle

Suppose a wave packet if formed by combination of two waves having same amplitude ‘a’
but different angular frequencies ω and ω’ and wave numbers k & k’.
The wave equation for these two waves can be represented as:
y1 = a cos (ωt-kx)…………………..[1]
y2 = a cos (ω’t-k’x)………………….[2]
According to principle of superposition the resultant wave motion at any point x and at time t is
given by:
Y=y1+y2
Y= a [cos(ωt-kx)+ cos (ω’t-k’x)]…………………….[3]
Using identity,
(𝑐+𝑑) (𝑐−𝑑)
cos c+cos d= 2 cos 2
cos 2

So in equation 3, c= (ωt-kx) & d= (ω’t-k’x)

 (ωt−kx)+(ω’t−k’x) (ωt−kx)−(ω’t−k’x)
Y= 2a cos cos
2 2

(ω+ω’)t−(k+k’)x (ω−ω’)t−(k−k’)x
= 2a cos 2
cos 2

Let ω + ω’ ≅ 2ω & 𝑘 + 𝑘’ ≅ 2𝑘
ω − ω’ k − k’
= ∆ω & = ∆𝑘
2 2
∆ωt−∆𝑘𝑥
Y= 2a cos (ωt − kx) cos 2
…………………………[4]
∆ωt−∆𝑘𝑥
Where amplitude of wave packet = 2acos 2
and phase = cos (ωt − kx)

The particle resides anywhere in wave packet. Thus the particle may be found between the two
consecutive nodes. The condition for nodes is;
∆ωt−∆𝑘𝑥
2acos 2
=0
∆ωt−∆𝑘𝑥1 𝜋
Or 2
= (2𝑛 + 1) 2 for n=0,1,2, -----------[5]
∆ωt−∆𝑘𝑥2 𝜋
Or = (2𝑛 + 3) ----------------------[6]
2 2

Subtract eq 6 and 5
∆𝑘(𝑥2 −𝑥1 )
Or 2
= −𝜋

2𝜋
∆𝑥 =
∆𝑘
Opertors
It is the rule by which a given function can be changed into another function. Each measurables like
energy, momentum etc is called observables. Each observable have an operator associated with it.
Let if A is operator corresponding to observable a then,
Aψ = aψ
So wavefunction here is called eigen function and observable is called eigen value and equation is
called eigen value equation.
Energy and Momentum Operators.
Let the wavefunction is given by
𝑥
Ψ=A𝑒 −𝑖𝜔(𝑡−𝜐)
Since ω=2πυ, v=υλ, E=hυ, λ=h/p
𝑖(𝐸𝑡−𝑝𝑥)
−
So, ψ= A𝑒 ℏ ………………1
This is wave equation for free particle.
Partially differentiate equation (1) w.r.t. ‘t’
𝑖
𝜕𝜑 𝑖
𝜕𝑡
= -iħ 𝐸A𝑒 −ħ(𝐸𝑡−𝑝𝑥)
𝑖
=-iħ 𝐸𝜑
𝜕𝜑
𝐸𝜑 = 𝑖ħ
𝜕𝑡

𝜕
𝐸 = 𝑖ħ 𝜕𝑡

This is energy operator.

Now partially differentiate equation (1) w.r.t. ‘x’
−𝑖
𝜕𝜑 𝑖
𝜕𝑥
= ħ 𝑝A 𝑒 ħ (𝐸𝑡−𝑝𝑥)
𝑖
= ħ 𝑝𝜑

ħ 𝜕𝜑
𝑝𝜑 =
𝑖 𝜕𝑥
ħ 𝜕
𝑝=
𝑖 𝜕𝑥
This is momentum operator.
Note: - Operators tells what operation to carry out on the quantity following it. Hence 𝜑is called
𝜕
eigen function of operators 𝑖ħ and E is called corresponding eigen value.
𝜕𝑡

Schrodinger Wave Equations

These equations are the fundamental equations of quantum mechanics. Schrodinger
equation helps to determine the motion of atomic particles just like Newton’s laws help to
study the motion of a classical particle. These equations help to determine the position
energy, momentum and wave nature of particle.
Schrodinger time independent wave equation:
ℎ
Consider a particle of mass m associated with wave of wavelength λ=𝑚𝑣. Let 𝜑be the wave
function having coordinates (x,y,z,t) associated with it.
The classical wave equation of motion is
𝜕2 𝜓 𝜕2 𝜓 𝜕2 𝜓 𝜕2 𝜓
= 𝑣 2 ( 𝜕𝑥 2 + 𝜕𝑦 2 + 𝜕𝑧 2 )=𝑣 2 ∇2 𝜓 …………….1
𝜕𝑡 2

𝜕2 𝜕2 𝜕2
Where, ∇2 = (𝜕𝑥 2 + 𝜕𝑦 2 + 𝜕𝑧 2 ) = Laplacian operator

𝑣 = velocity of the particle.

The solution of the equation (1) is
ψ= 𝜓0 𝑠𝑖𝑛𝜔𝑡 = 𝜓0 𝑠𝑖𝑛2𝜋𝜈𝑡 …………….2
ν is the frequency of the wave associated with wave.
Differentiating equation (2) w.r.t. ‘t’ twice
𝜕2 𝜓
= - 𝜓0 (2𝜋𝜈)2 𝑠𝑖𝑛2𝜋𝜈𝑡
𝜕𝑡 2

−4𝜋 2 𝑣 2 𝜓
= - 4𝜋 2 𝜈 2 𝜓 = (Since v=νλ)…………3
𝜆

Put the values of equation (3) in equation (1).

−4𝜋2 𝑣 2 𝜓
𝑣 2 ∇2 𝜓 = 𝜆

4𝜋 2 𝜓
∇2 𝜓 + = 0 ………………………4
𝜆2

Now we know that

ℎ
λ =𝑚𝑣
 4𝜋 2 𝑚2 𝑣 2 𝜓
so, ∇2 𝜓 + = 0 …………………5
ℎ2

Since ,
Total energy E = Kinetic energy + Potential energy
1 𝑚2 𝑣 2 𝑝2
= 2 𝑚𝑣 2 + 𝑉 = +𝑉 = +𝑉
2𝑚 2𝑚

𝑚2 𝑣 2 = 2𝑚(𝐸 − 𝑉) ……………..6
Put values of equation (6) in equation (5).
4𝜋 2
∇2 𝜓 + 2𝑚(𝐸 − 𝑉)𝜓 = 0
ℎ2

8𝜋 2 𝑚(𝐸−𝑉)𝜓
∇2 𝜓 + =0
ℎ2

2𝑚(𝐸−𝑉)𝜓
∇2 𝜓 + =0 ………………7
ℏ2

Equation (7) is called Schrodinger’s independent wave equation.

For a free particle V=0
2𝑚𝐸𝜓
Therefore, ∇2 𝜓 + =0
ℏ2

This is Schrodinger’s time independent wave equation for free particle.

Schrodinger time dependent wave equation

Let 𝜓 be the wave function associated with moving particle. This is a complex function of
space and time coordinates.
The differential equation representing a 3 dimensional wave motion is
𝜕2 𝜓
= 𝑣 2 ∇2 𝜓 ………………….1
𝜕𝑡 2

Solution of equation (1) is

𝜓(𝑥,𝑦,𝑧,𝑡) = 𝜓0(𝑥,𝑦,𝑧,𝑡) 𝑒 −𝑖𝜔𝑡

𝜓 = 𝜓0 𝑒 −𝑖𝜔𝑡 …………………………….2
Differentiating equation (2) w.r.t. ‘t’
𝜕𝜓
= 𝜓0 (−𝑖𝜔) 𝑒 −𝑖𝜔𝑡
𝜕𝑡
= 𝜓0 (−𝑖2𝜋𝜈) 𝑒 −𝑖𝜔𝑡
 = −2𝜋𝑖𝜈𝜓
𝐸
= −2𝜋𝑖 ( ℏ ) 𝜓
−𝐸𝜓 ℎ
= (Since E=hν & ℏ=2𝜋)
ℏ
𝜕𝜓
Or, 𝐸𝜓 = 𝑖ℏ 𝜕𝑡 ………………………………3

Put the value of 𝐸𝜓 in time independent wave equation

2𝑚 𝜕𝜓
∇2 𝜓 + [𝑖ℏ 𝜕𝑡 − 𝑉𝜓] = 0
ℏ2

2𝑚 𝜕𝜓
Or, ∇2 𝜓 = − [𝑖ℏ 𝜕𝑡 − 𝑉𝜓]
ℏ2

ℏ2 𝜕𝜓
− 2𝑚 ∇2 ψ + Vψ = iℏ 𝜕𝑡 …………………………4

This is Schrodinger’s time dependent wave equation in 3 dimension.

In one dimension,
ℏ2 𝜕 2 ψ 𝜕𝜓
− 2𝑚 𝜕𝑥 2 + Vψ = iℏ 𝜕𝑡 ……………………….5

Application of Schrodinger Wave Equations

Particle in One dimensional box
Consider a particle trapped in a 1 D box with infinitely hard walls which reflects the
electron back in the box, keeping its total energy constant.
This electron can move along x- axis between x=0 to x=L.
The potential energy of particle is defined as
V=0 for 0≤ 𝑥 ≤ 𝐿
V= ∞ 𝑓𝑜𝑟 0 < 𝑥 < 𝐿
Schrodinger wave equation for this particle is
𝜕2 𝜓 2𝑚
+ 𝐸𝜓 = 0 …………………….1
𝜕𝑥 2 ℏ2
2𝑚𝐸
Let = 𝑘2 ……………………..2
ℏ2

So equation (1) becomes

𝜕2 𝜓
+ 𝑘2𝜓 = 0
𝜕𝑥 2
The solution of equation (3) is
𝛹 = Asinkx+Bcoskx………….4
Where A, B and k are constants whose values are to be determined applying boundary
conditions.
Apply first boundary condition to equation (4)
i.e. 𝛹 = 0 𝑎𝑡 𝑥 = 0
so, 0 = Asink.0 + Bcosk.0
or B=0
Applying 2nd boundary condition to equation (4)
i.e. 𝛹 = 0 𝑎𝑡 𝑥 = 𝐿
So, 0= AsinkL+BcoskL
Or AsinkL=0
Since A≠ 0
Therefore, sinkL= 0= sin nπ
kL=nπ
nπ
or k= 𝐿

𝑛2 𝜋 2
Or, 𝑘2 = ………………………5
𝐿2

Now compare equation (2) and (5)

2𝑚𝐸 𝑛2 𝜋 2
=
ℏ2 𝐿2
𝑛2 𝜋 2 ℏ2
Or, 𝐸 = 2𝑚𝐿2

This equation shows that particles in a well can take only certain energy values
corresponding to n=1,2,3….. E is called energy eigen value.
Putting the values of B & k is equation (4)
𝑛𝜋𝑥
Ψ = Asin 𝐿

We will use normalisation condition to find value of A.

𝐿
∫ |𝜓|2 𝑑𝑥 = 1
0
Or,
𝐿
𝑛𝜋𝑥
∫ 𝐴2 𝑠𝑖𝑛 𝑑𝑥 = 1
0 𝐿
𝐿
2
1 2𝑛𝜋𝑥
𝐴 ∫ (1 − 𝑐𝑜𝑠 ) 𝑑𝑥 = 1
0 2 𝐿
𝐿
𝐴2 [ ] = 1
2

2
𝐴=√
𝐿

Putting this value of A in equation (6)

2 𝑛𝜋𝑥
𝛹 = √ sin
𝐿 𝐿

This is normalised wave function equation.

The first three energy eigen function & their probability densities are shown as: