WAVEMECHANICS

Importance of Wavemechanics

In Classical Mechanics we can explain motion of a body with the help of Newton’s Laws of
motions: 1. Law of inertia, 2. Law of force, 3. Law of action and reaction. In this case we
have to remember that body can be terrestrial, planet, starts etc (very large) and also it can be
microscopic. The speed of bodies should always be much less than velocity of light, v<<c.

However, Classical Mechanics can not explain

1. The motion of subatomic particles, atomic particles, molecules
2. Blackbody spectra
3. Discrete spectrum of atoms (According to classical mechanics energy changes will be
continuous)
4. Variation of specific heats of metals and gases

Planck’s hypothesis of discretization of radiation:

According to this hypothesis the radiation is emitted or absorbed by matter in the form of
discrete packets or energy quanta (hν), where h being the Planck constant

*This concept is also not fully satisfactory. Later Heisenber introduced matrix mechanics and
Schroedinger developed wave mechanics.

In this concept he combined the classical wave theory and wave particle duality. With this
theory many atomic physics problems solved.

Wave particle duality, de Broglie waves:

He proposed a fundamental relationship between waves and particles

● If a particle has momentum p then its motion is associated with a wave of wavelength λ
according to λ = h/p
● If there is a wave (λ
λ) then a particle may be observable with momentum p according to p =
λ
h/λ
● Wave nature of light explains the phenomena like interference,
Diffraction and polarization
● It can not explain photoelectric effects, Compton effects, Characteristic x-ray spectrum, and
black body radiation.
● Dual nature of the wave successfully explains the above phenomena. This is called wave
particle duality

Photons are charge less, have zero rest mass and spin 1.
Photons have momentum p = E/c = hν/c, Mass = hν/ c2, Spin: 1
PHOTOELECTRIC EFFECTS
It is the phenomenon of ejection of electrons from the surface of a metal (usually) in response
to incident light.

● One quantum will be absorbed by one

electron. The electron has to overcome work
function energy Wo to come out from the
surface.
● The incident photon energy (hν) will be
spent to overcome the work function energy
and the rest amount will be spent in the form
of kinetic energy (Ek) of the ejected
electrons. Ek = hν
ν−Wo
● Threshold frequency: νo = Wo/h
• Light having frequency less than the threshold Fig. Experimental arrangement of
frequency can not eject electrons, no matter realising photoelectric effect
how intense the light is.
● The collector is kept at positive potential while electrode at zero potential.
● The ejected electrons will be collected at the collector, and increase positive potential will
increase the current through the circuit.
● At some positive potential all the ejected electrons will be collected, therefore current will
show saturation trend.
● The collector is kept at negative potential while electrode at zero potential.
● The ejected electrons will be repelled by the collector, and increase negative potential will
decrease the current through the circuit.
● At some minimum negative potential all the ejected electrons will be rejected, therefore
the potential at which the current is just zero is called stopping potential.
● Stopping potential does not depend on the light intensity, depends on frequency of
incident light. Highest kinetic energy of the ejected electrons will be equal to stopping
potential energy. Ek = ½ mv2 = eVs, where, Vs is the stopping potential

● At constant
frequency the
photoelectric
current increases
with increasing
incident light
intensity

● No time lag between light illumination and ejection of electrons

● Maximum Ek is independent of intensity of incident light.
● Stopping potential is same for all intensity for a fixed frequency (figure left side)
● Stopping potential varies depending upon the light frequency (figure right side)
Calculation of Planck constant using Photoelectric effects:

ν− W o
Ek = hν

● From the relation between the kinetic energy and the

incident light frequency plot one can calculate Planck
constant h from the slope.
● There are different intercepts which correspond to
different work function energy corresponding to
different metals.
● Photoelectric effect is the most direct and convincing
evidence of the existence of the corpuscular nature or particle nature of light. It is the
evidence of quantization of electromagnetic field.

COMPTON EFFECT
The phenomenon of inelastic scattering of X-ray by loosely bound electrons resulting in the
modification of the scattered X-ray. The wavelength of scattered X-ray is larger than that of
incident X-ray.

Theoretical explanation:
● Photon of energy E = hν ν and
momentum p = h/λ λ collides
with electron at rest
● After collision electron is
recoiled with momentum mv at
a direction φ as in figure.
Relativistic mass of electron is
m (rest mass m0).
● Photon scattered at an angle θ.

● Conservation of energy and momentum

…… (2)
gives

………(1)

.… (3)
Squaring and adding eqn 2 and eqn 3 we get

………(4)

Squaring and simplifying eqn 1 we get

………(5)

………(6)

………(7) This is the expression

for Compton shift: ∆λ

Experimental Verification:

Experimental arrangement is as shown below. The detector detects the signal at various
scattering angle and the intensity is plotted with respect to wavelength as in figure.

Detector
′
hν
hν
θ

Photon source

● Monochromatic X-ray falls on

graphite target and the scattered X-ray
is detected at different angle using
Bragg X-ray diffractometer. The
intensity distribution of at some specific
angle is shown in the figure.
● When θ = 0 the radiation is
unmodified.
● For, θ = 45 deg, 90 deg and 135 deg
there are two peaks, one modified and
the other unmodified. ∆λ is Compton
shift.
● For greater θ shift is more.
● Maximum shift: 2h/ m0c = 0.048Å.
∗ Why Compton Effect is not observable with visible light?
It is known now that the maximum Compton shift, ∆λ: 2h/ m0c = 0.048Å

With X-ray, say λ= 1 Å………

The % shift is = [∆λmax/λ] x 100 = [[2h/ m0c]/λ] x 100 = [0.048/1] x 100 = 4.8%

With visible light, say λ= 6000 Å….

The % shift is = [∆λmax/λ] x 100 = [[2h/ m0c]/λ] x 100 = [0.048/6000] x 100 = 0.0008%

Thus, with visible light the %shift is very small, and hence it would be difficult to detect.

Pair Production

When a photon of high energy passes near the field of nucleus, it materializes into an electron
and positron. This phenomenon is known as pair production.

•In this process charge, energy and

momentum remains conserved.
•The rest mass energy of an electron or
positron is 0.51 MeV (according to E = m0
c2).
•Minimum energy of photon to create a
pair 1.02 MeV. The corresponding photon
wavelength = 1.2 pm.
• This wavelength corresponds to gamma
ray photons.
• Excess energy of photon will be the kinetic energy of the electron and positron created.

Pair Annihilation

In this process, an electron and a positron interact with each other and annihilate to be
converted to electromagnetic energy in the form of two γ-ray photons.

The conservation of charge, energy and momentum must be valid. Two γ-photons are
produced in this process. Each has energy of [0.51 MeV +1/2 K.E.] Here K.E. is the total
kinetic energy of the electron and positron.

Pair production cannot occur in empty space

Suppose without nucleus pair production is possible, then the conservation of momentum and
energy can give us the following expression---
Conservation of energy:

hν=2m0 c2/[1-v2/c2]0.5 …………(1)

Conservation of momentum:

h/λ= [2m0 v/[1-v2/c2]0.5] cosθ

hν = [2m0 c2(v/c)/[1-v2/c2]0.5] cosθ
or,
hν = 2m0 c2/[1-v2/c2]0.5 [(v/c)]cosθ ……..(2)

The factor [(v/c)]cosθ is < 1, thus, hν < 2m0 c2/[1-v2/c2]0.5 ……(3)

Eqn-1 and Eqn-3 contradict to each other. Hence energy and momentum can not be conserved
simultaneously. Thus, it is not possible for pair production to conserve both, energy and
momentum unless some other object is involved to carry away part of the initial photon
momentum. Therefore pair production cannot occur in empty space.

Therefore pair production cannot occur in empty space.

Phase velocity and Group velocity of a wave:

•An individual monochromatic wave moving with a velocity vp known as phase velocity.
•A group of waves moving with velocity vg known as group velocity.
•A group of waves or wave packet is the superposition of more than one wave.

A plane harmonic wave traveling with frequency ω in the + x direction can be written as:

y = a sin [ωt-kx]
= a sin [2πνt – (2π/λ)x]

For an instant t+∆t the wave travels x+∆x

y = a sin [2πν(t+∆t) – (2π/λ)(x+∆x)]
For a plane harmonic wave traveling with constant phase we can write,
2πνdt - 2π/λdx = constant =dΦ
2πν-(2π/λ)dx/dt = dΦ/dt = 0
ω.dt- k.dx = 0 OR, dx/dt = vp = ω/k

Group velocity vg of a wave packet or group of waves:

Let there are two plane waves of same amplitude but with different frequency superimpose
onto each other
y1 = a sin (ω1t-k1x)
y2 = a sin (ω2t-k2x)
The resultant wave can be written as
y = a sin (ω1t-k1x) + a sin (ω2t-k2x)
y = a [sin (ω1t-k1x) + sin (ω2t-k2x)]
= 2a [sin {(ω1+ ω2)t/2 - (k2+k1)x/2}cos{(ω1- ω2)t/2 + (k2-k1)x/2}]
= 2a [sin (ωt-kx) cos (∆ωt/2 +∆kx/2)]

It is assumed that (ω1+ ω2)/2 = ω and (k1+ k2)x/2 = k

y = 2a [sin (ωt-kx) cos (∆ωt/2 +∆kx/2)]

The above wave represents two waves

I. One wave travels with velocity
vp = ω/k = νλ
II. The other travels with velocity vg = ∆ω/∆ ω/dk. This velocity is the velocity of the
∆k = dω
envelop (dotted curve) of the groups of waves (solid red curve) of wave packet.

Phase velocity and de-Broglie wave

We know phase velocity vp = ω/k……..[1]
If particle has velocity v then the associated wave velocity should also have velocity = vg = v.

According to de-Broglie relation

λ=h/mv ……………….[2]
Now, vp = ω/k = (2πν)/(2π/λ) = νλ
Hence, vp.vg = (νλ)*(h/mv) = hν/m = E/m = mc2/m = c2

OR, vp.vg = c2 ……………[3] [relativistic case]

In non-relativistic case:
vp.vg = (νλ)*(h/mv) = hν/m = E/m = ½ mv2/m = ½ v2 = ½ vg2
Or, vp = vg/2

Relation between phase velocity and group velocity of a wave

vg = dω/dk
= d(kvp)/dk = vp + k d(vp)/dk = vp + [2π/λ] d(vp)/d(2π/λ)
vg = vp - λ dvp/dλ

Particle diffraction: Wave nature of light: Davison Germer Experiment

• This experiment proves that if particles have wave nature,

then they should exhibit diffraction as electromagnetic
wave does. It proves the de Broglie hypothesis.
2θ+φ = 180o
θ = [180o – 50]/2 = 65o

de Broglie wavelength associated with an electron

accelerated through V volts is

X-ray crystal diffraction analysis shows that for θ =

65o the Bragg diffraction equation 2d sin θ = nλ
gives λ = 1.67Å for n=1 order and nickel crystal d spacing value 0.91Å.

Thus it is verified that electrons have wave nature. De Broglie hypothesis of wave particle
duality is proved.

Uncertainty Principle: Heisenberg Uncertainty Principle

• It is impossible to determine the exact position and momentum of a particle simultaneously.

• The product of uncertainties in determining the position and momentum of a particle at the
same instant is of the order of ħ.
∆x.∆px ≈ ħ

• The product of uncertainties in determining the position and momentum of a particle at the
same instant can never be small than ħ/2.
∆x.∆px ≥ ħ/2

• Uncertainty principle has no physical significance for macroscopic (large) objects.

• The uncertainty principle is application to other canonically conjugate physical quantities
such as energy and time, angular momentum and angle.
∆E.∆t ≥ ħ/2
and ∆J.∆θ ≥ ħ/2

Proof of uncertainty relation: Determination of position by microscope

Let us consider that photon collides with electron resulting in
recoil of electron. Along the x-axis suppose we want to measure
accurately the position and momentum of an electron using an
ideal microscope which is free from all mechanical and optical
defects.

We assume that recoil electron has momentum along the x-axis

as px as in figure. Scattered photon can enter the microscope
with maximum angle θ with x-component of momentum = p
sinθ.

The maximum change in the photon momentum can be calculated from conservation of
momentum along x-direction.
Thus, in one event of photon-electron collision (bold red scattered photon) we can write, h/λ
= [h/ λ′] sin θ + px1 ………….[1]

In the other event of photon electron collision, we can write, h/λ = -[h/ λ′] sin θ + px2
………….[2]

From (1) and (2) we can write, [h/ λ′] sin θ + px1 = -[h/ λ′] sin θ + px2 ….[3]
Or, , [h/ λ′] sin θ + px1 = -[h/ λ′] sin θ + px2 ….[4]
Or, ∆p = px2 - px1 = 2[h/ λ′] sin θ ………[5]
Position of the electron can be measured with minimum uncertainty ∆x.

At limiting condition i.e. at highest resolution of the microscope ∆x takes the form
∆x = λ′/2sinθ……………….[6]

Thus, the product of two uncertainties gives the result as:

∆x ∆p = λ′/2sinθ * 2[h/ λ′] sin θ ………….[7]

OR, ∆x ∆p = h………………..[8]
OR, ∆x ∆p > ħ/2 hence proved the uncertainty principle

Applications of Heisenberg Uncertainty Principle

Using uncertainty relation we can prove some physical phenomena, such as I) non-existence
of electrons within the nucleus, II) concept of Bohr orbit with constant energy.

I) Electron can not exist within the nucleus

Typical nucleus radius of atom is ≈ 5 x10-15 m

This can represent the maximum uncertainty in the position, thus, ∆x= 2x5 x10-15 m
The minimum uncertainty in the momentum of electron if exits within the nucleus will be ∆p,
which will be the minimum momentum of electron = p

Thus, p=ħ/2∆x = h/4π∆x = 0.52x10-20 kg-m/s

Thus, K.E. (relativistic) = p.c ≈ 10 MeV

Thus, to be part of the nucleus the electron must have minimum energy of 10 MeV.

From experimental evidence it is known that unstable radioactive nuclei emits electrons (β-
particles) that have highest energy 3-4 MeV.
This evidence infer that electrons can not exist within the nucleus

II) Concept of Bohr orbit with constant energy is incorrect.

According to this concept of Bohr orbit, energy of an electron in a orbit is constant i.e. ∆E =
0. Inferring: all energy states of the atom must have an infinite life-time.

Experimental evidence: excited states of a atom have life-time ~ 10-8 sec.

• Finite life-time τ results in a finite energy width (energy uncertainty).

Now, E= p2/2m
Or, ∆E = (p/m)∆p
= (2p/m)ħ/(2∆x)
= (mv/mx)ħ
= ħ/(x/v)
= ħ/τ
∆E = 0 means, τ = ∞ (infinite)

Using uncertainty principle calculate binding energy of an electron in an atom

Binding energy of an electron in an atom depends on the radius of the orbit

in which it revolves.
Let us consider that electron orbital radius is r.
Then uncertainty in the position will be ∆x = 2r
The corresponding uncertainty in the momentum is
∆p = ħ/2r, this gives the minimum momentum p = ħ/2r

Using non-relativistic momentum of an electron we can write the K.E. of the electron as K.E.
= p2/2m = h2/[32π2mr2]
The potential energy of the electron in the field of nucleus of atomic number z
as V = -ze2/[4πεr]

Thus, total energy of the electron in the orbit is

E = K.E. + V = h2/[32π2mr2] - ze2/[4πεr]
≈ 10-20/r2 – 15z x10-10/r eV [ we have assumed ε = 8.854 x 10-12 F/m]
If we take the radius ~ 10-10 meter
Then, E = 1-15z eV

For H-atom with z=1 , get E ~ 14 eV, which is comparable to the experimentally measured
energy as 13.6 eV.
Thus, binding energy calculated using uncertainty relation is comparable to the measured
value.

Using uncertainty principle calculate ground state energy of linear harmonic oscillator

Using non-relativistic approach we can write total energy of a linear harmonic oscillator
E = K.E. + P.E.= p2/2m + ½ kx2
E = (∆p)2/2m + ½ k(∆x2 ) [p≈∆p, and x≈∆x]
E = (ħ/2∆x)2/2m + ½ k(∆x2 ) [∆p∆x≈ħ/2]
For minimum energy ∂E/∂∆x = 0
Thus, (ħ2/8m)(-2)/(∆x)3 +k∆x = 0
Or, (ħ2/4m)/(∆x)3 –k(∆x) = 0
Or, (ħ2/4m) = k(∆x)4
Or, (ħ2/4m) = k(∆x)4
Or, (∆x)2 =ħ/(4mk)0.5
Or, (∆x)2 =ħ/2(mk)0.5
E = (ħ/2∆x)2/2m + ½ k(∆x2 )
Or, E = (ħ2/8m)/ [ħ/2(mk)0.5] + ½ k ħ/2(mk)0.5
Or, E = (ħ/4m)[(mk)0.5] + ½ k ħ/2(mk)0.5
Or, E = (ħ/4)[(k/m)0.5] + (¼) ħ(k/m)0.5
Or, E = (ħ/4)ω+ (ħ/4)ω
Or, E = (ħ/2)ω
Or, E = ħω/2
This is the zero point or minimum energy of a linear harmonic oscillator

Two slits particle interference and particle nature of light: [Thought experiment]
• In a double-slit apparatus, if one sends particles through the apparatus one at a time it will
result in a single particle appearing on the screen, as expected.
• When the particles are allowed to build up one by one, an interference pattern is seen on to
the screen.
•The observed interference pattern suggest that each electron interfere with itself, which is
true if the electron goes through both slits at the same time!

• This phenomenon is
observed by performing
experiments with atoms and
molecules.

• These experimental
evidences tell us that
electrons, protons, neutrons, and even larger entities that are ordinarily called particles
nevertheless have their own wave nature and even their own specific frequencies.

Electron Microscope:

Electron microscope is a microscope which utilize electrons beam to create an image of an

object. With this microscope one can go to very high magnification and resolution, thus
enabling imaging of very small object (nanometer dimension).

Type of electron microscope: I). Transmission Electron Microscope () and II). Scanning
electron Microscope (SEM). TEM

TEM: • In TEM primary electron beam partially transmitted through a very thin
(semitransparent for electrons). The transmitted beam carries the information of the structure
of the specimen. The spatial variation in this information (the "image") is then magnified by a
series of magnetic lenses. Finally the beam hits a fluorescent screen, photographic plate, or
light sensitive sensor such as a CCD (charge-coupled device) camera. The image detected by
the CCD may be displayed in real time on a monitor or computer.

SEM • In Scanning Electron Microscope (SEM) the image is produced by detecting

secondary electrons which are emitted from the surface due to excitation by the primary
electron beam. In this case, electron beam is scanned across the surface of the sample with
detectors building up an image by mapping the detected signals with beam position.
Magnification: 10 to 500,000 times:
times ~1 nm to 5 nm
Resolution < 1 nm and Magnifications > 50000000 times

Optical microscope magnification

nification: 500, Resolution: 200 nm
Wave function:
A quantity associated with matter waves varies periodically called wave function. It is
represented by Greek Letter Ψ. It has no direct physical significance. However, Ψ is related
to the probability (ρ) density of finding the particle (matter) at a given space and time and ρ
can be expressed as-

ρ = ΨΨ* …………………[1]

Usually Ψ is complex and can be expressed as

Ψ = A + iB ……………….[2]
The complex conjugate of Ψ
Ψ* = A – iB ………………..[3]

Hence, probability density ρ = ΨΨ* = A2 +B2

Total probability of finding the particle over the entire spare will be unity
+∞
Hence, ρT = ∫-∞ ΨΨ* dV = 1

Properties of Wave Function:

I). Ψ must be finite, continuous and single valued. Ψ can not take infinite values as the
probability of finding the particle would be infinite, which is incorrect.
II). Derivative of Ψ i.e. ∂Ψ/∂x, ∂Ψ/∂y, ∂Ψ/∂z must be finite, continuous and single valued.
III). Ψ must be normalizable.

Schroedinger time independent wave equation:

Let us consider a matter wave represented by Ψ as

Ψ (x,y,z, t) = Ψ0 (x,y,z) e-iωt = Ψ0 (x,y,z) e-iEt/ħ

and satisfy the wave equation-

∂2Ψ/∂x2 + ∂2Ψ/∂y2 +∂2Ψ/∂z2 = [1/vp2] ∂2Ψ/∂t2 …….[1] where vp = phase velocity

Or, in term of Laplacian operator ∇ the equation [1] can be written as

∇2Ψ = [1/vp2] ∂2Ψ/∂t2 …………[2]

Differentiating equation-1 w.r.t time, we get

R.H.S. = [1/vp2][-iE/ħ]2Ψ = -ω2/ vp2Ψ = -k2Ψ = -[ħ2k2/ħ2]Ψ = -p2/ħ2Ψ

Now, E = p2/2m +V
or, p = [2m(E-V)]0.5
Therefore, R.H.S. = -[2m/ħ2][E-V]Ψ
Thus, equation –1 can be written as, ∇2Ψ + [2m/ħ2][E-V]Ψ
Ψ = 0 …………[3]

Now, Ψ can be considered as only function of (x,y,z) thus the equation-3 represents the time
independent Schroedinger equation.

Schroedinger time dependent wave equation:

Ψ (x,y,z, t) = Ψ0 (x,y,z) e-iωt = Ψ0 (x,y,z) e-iEt/ħ

∂Ψ/∂t = [-iE/ħ]Ψ

Or, EΨ = iħ∂Ψ/∂t

Let us consider the equation

∇2Ψ + [2m/ħ2][E-V]Ψ = 0

∇2Ψ + [2m/ħ2][ iħ∂Ψ/∂t -VΨ] = 0

∇2Ψ + [2m/ħ2][-VΨ] + [2m/ħ2]iħ∂Ψ/∂t = 0

[ħ2/2m] ∇2Ψ - VΨ + iħ∂Ψ/∂t = 0

[(ħ2/2m) ∇2 – V]Ψ = -iħ∂Ψ/∂t

[-(ħ2/2m) ∇2 + V]Ψ = iħ∂Ψ/∂t …………….[4]

This is known as Schroedinger time dependent wave equation.

Quantum mechanical Operator:

An operator is a mathematical term which upon operating on a function changes the function
to another function. Example:

ϕ (x,y,z) = P Ψ (x,y,z)

Ψ (x) = A sin kx, and P = -iħ

P [A sin kx] = -iħ [A sin kx] = -iħ A cos kx = B ϕ (x)

Classical quantity Quantum mechanical operator

I] x, y, z
I] position: x, y, z II] -iħ , -iħ -iħ
II] momentum, px, py, pz
III] energy E III] iħ
IV] K.E.
V] Hamiltonian (K.E. +V.E.) IV] IV]
Eigen values and Eigen function

An operator operating on a function may leave the function unchanged but with a real or
complex multiple.

P Ψ (x,y,z) = A Ψ (x,y,z)
Here, Ψ is an eigen function and A is eigen value
HΨ = EΨ, where , H is Hamiltonian operator, E eigen value and Ψ eigen function

If eigen value is real then the operator is said to be Hermitian operator

Linearity and Superposition of eigen states

If Ψ1 and Ψ2 are two possible wave function of an operator P having same eigen values E,
then any linear combination of Ψ1 and Ψ2 will also be a possible wave function of P.

P Ψ1 (x,y,z) = E Ψ1 (x,y,z) and, P Ψ2 (x,y,z) =E Ψ2 (x,y,z)

if Ψ = AΨ1 (x,y,z) +B Ψ2 (x,y,z)

Then PΨ = P[AΨ1 (x,y,z) +B Ψ2 (x,y,z) ] = A E Ψ1 + BE Ψ2 = E [AΨ1 + BΨ2 ]
Or,
PΨ = EΨ, thus Ψ is also a eigen function.

Expectation values

Expectation value of a parameter, such as position operator is given by

Particle in a box
Wave function of the particle in the box (Normalization)

Variation of Wave Function and Probability of the particle in the box