Classical Mechanics

What is classical Mechanics?

Classical mechanics is the study of the motion of bodies including the special
case in which bodies remain at rest.

Classical mechanics has many important applications in other areas of

science, such as Astronomy (e.g., celestial mechanics), Chemistry (e.g., the
dynamics of molecular collisions), Geology (e.g., the propagation of seismic
waves, generated by earthquakes, through the Earth's crust), and Engineering
(e.g., the equilibrium and stability of structures).

Classical Mechanics is based on the fundamental principles of Newton’s

law.

Classical Mechanics is applicable to macroscopic (larger) particles.

Maxwell’s electromagnetic wave theory is the basis of classical mechanics.
According to this theory any amount of energy absorbed or emitted is continuous.

Classical Mechanics defines the state of the system with certainty.

Limitation of Classical Mechanics

 Photoelectric Effect
According to this theory, light of fixed frequency ν consists of a collection of indivisible
discrete packages, called quanta, whose energy is E = hν

Quantum tunneling
Quantum tunneling is a phenomenon where particles may "tunnel through" a barrier
which they have insufficient kinetic energy to overcome according to classical mechanics.
Tunneling is a result of the wavelike nature of quantum particles.
Black Body Radiation

One experimental phenomenon that could not be adequately explained by classical

physics was black-body radiation. Hot objects emit electromagnetic radiation.

The Uncertainty Principle

Heisenberg uncertainty principle states that the position and the velocity of an
object cannot both be measured exactly, at the same time.
Δx.Δp ≥ h/4π

De Broglie waves can be experimentally observed

De Broglie proposed that electron (or matter) also has a dual character as a wave
and as a particle.
λ = h/mv
 Quantum Mechanics

To explain the physical properties of nature at the scale of atomic and subatomic level,
physicist introduced the fundamental theory of Quantum Mechanics.

What is Quantum Mechanics ?

Quantum Mechanics explains the nature of a particle at microscopic (atomic and

subatomic) scale.

Heisenberg’s uncertainty principle and de Broglie’s concept of dual nature of

matter(particle nature and wave nature) are the foundation of quantum mechanics.

Plank’s quantum theory is the basis of quantum mechanics. According to this theory
energy absorbed or emitted discontinuously in the form of packets i.e. quantum.
E = hv

Quantum Mechanics provides the possibility of finding the particle in space.

 Schrodinger Wave Equation
 Erwin Schrodinger proposed that If electron is wave like, then its should obey the
equation of wave motion like other waves in a motion. On the basis of this simple idea
he substituted the value of de-Broglei relation (λ = h/mv) into classical equation of wave
motion. Thus the equation obtained describes the wave motion of one electron and is
called the schrodinger wave equation.

Where E = total energy of the electron i.e. Kinetic energy + potential energy
V = potential energy of the electron
m = mass of the electron
h = Plank’s constant
ψ = wave function and is amplitude of electromagnetic wave
The Schrodinger wave equation can also be expressed as

Where is called Laplacian operator

 Derivation of Schrodinger Wave Equation

Schrodinger wave equation can be derived from de-Broglei idea of dual nature
of the matter applied to an electron.

Total energy of electron (E) = Kinetic energy + Potential energy

……….. (1)

From de-Broglei equation

or ……….. (2)

Where m is the mass of electron, v is the velocity of electron and h is Plank’s constant.
 Derivation of Schrodinger Wave Equation
Substituting the value of mv from equation (2) to equation (1)

or ……….. (3)

In quantum mechanics matter can be considered as a wave and equation of such a

wave of vibrating string can be represented as

……….. (4)

Where ψ is the wave function, x is the displacement, λ is the wavelength and

A is the amplitude of the wave.
Differentiating the function ψ in equation (4) with respect to x

……….. (5)

Differentiating the function ψ in equation (5) again with respect to x

……….. (6)
 Substituting the value of from equation (4) in equation (6), we get

……….. (7)

Substituting the value of from equation (3) in equation (7), we get

……….. (8)

When the electron moves in three dimensions i.e. x,y,z , then the equation (8) will become
 ……….. (9)

Equation (9) is a Schrodinger wave equation. This equation describes the relation
between wave function (ψ) and energy (E) of the electron. It is second order differential
Equation and can be solved for certain definite values of energy of the electron under
reference.
 Eigen Value

Equation (7) represents the Schrödinger wave equation which shows the motion of a
stationary wave in one direction .

It is clear from the above equation that a stationary wave in the stretched string
with amplitude function (ψ) can have significance only for a certain definite values of
wavelength (λ). The wavelength is related to total energy (E) as

Energy (E) is the function of wavelength i.e. each wave having definite wavelength
with definite value of energy.
 Eigen Value
Being a second order differential equation, the Schrodinger wave equation
can have number of solutions, many of them without any significance. But some
definite values of total energy (E) , the solution will certainly have significant
values.
The values of total energy (E) for which the wave equation can have significant
solution are called eigen values.
These eigen values corresponds to the discrete energy levels as postulated by Bhor.
The existence of atomic energy levels in an atom has been directly proved by
Schrodinger wave equation , which has given rise to the wave mechanical concept
of the atom.
The various value of (ψ) which have been derived from the wave equation
corresponding to definite values of energy (eigen values) are called eigen
functions.

Only those wave functions which satisfy certain conditions are acceptable. These
conditions are imposed on the wave equation as boundary conditions and can be
summarised as follows
(i) Ψ must be single valued and finite.
(ii) Ψ must be continuous.
(iii) Ψ must become zero at infinity.
 Physical significance of ψ and ψ2
The wave function (ψ) does not have any physical significance but it has only
mathematical significance. Normally the amplitude of any wave represents the
displacement of some property. for example amplitude in case of sound waves
corresponds to increase or decrease of air pressure relative to static pressure. But in case
of electron no such property is associated with the wave, as such amplitude of electron
wave have no physical significance..
In case of light or sound, the square of the amplitude of the wave at any point gives the
intensity of light or sound at that point. Similarly the square of the amplitude of the
electron (ψ2) at any point gives the intensity of the electron wave at that point. According
to Heisenberg uncertainty principle The intensity of electron at any point is interpreted
as probability of finding the electron at that point. So the ψ2 gives the probability of the
electron existing within small volume or space. This space is called atomic orbital.
The zero value of ψ2 at a fixed point means the probability of finding an electron at that
point is zero.
As the probability is directly related to the density of electron cloud, ψ2 gives the
electron density at any given point.
Characteristics of the wave function ψ

(i) It should be normalized wave function.

(ii) If there are more than one wave function than two wave function must be
Orthogonal to each other.

Normalized wave function

A wave function is said to be normalized if integration of ψ2 (i.e. ψψ*) with

Respect to element volume (dτ) over the whole range of space (− ∞ to + ∞) is
Equal to unity.

Mathematically it can be expressed as

If then ψ is not a normalized wave function.

Orthogonal wave function

The two wave function are orthogonal if they are different over the entire space.
In other words their description must be unique.
If there are two wave function ψ1 and ψ2 with complex conjugates ψ1* and ψ2*
respectively then the two wave function will be orthogonal to each other.

and
 Radial probability distribution Curves

The probability of finding the electron in a spherical shell of thickness dr at a

distance r from the nucleus is called radial probability. It is equal to the product
of the volume of the shell of thickness dr and the probability ψ2 per unit volume

r + dr

Radial probability = 4π2dr × ψ2 (radial probability density)

Required Volume = [volume of sphere with radius r + dr]− [volume of sphere with radius r]
= 4π/3(r +dr)3 − 4π/3r3
= 4π/3( r3 + 3r2 + 3rdr2 + dr3) − 4π/3r3
= 4π/3 (3r2dr) = 4πr2dr
It is more useful to study the radial probability at different distances from the
nucleus. The plots of radial probability versus distance from the nucleus are called radial
probability distribution curves.
dP(r) = g(r) dr (radial distribution function)
Ques 1.
For 1s hydrogen like

Calculate r max. and also show that if z increases, rmax. decreases i.e. rmax. is proprtional
to 1/z

Solution:
for maxima
 Hydrogen Atom
−e Hψ = E ψ

H = K.E. + P.E.
r
+Ze

………(1)

Polar Coordinate x +ꝏ to − ꝏ r 0 to − ꝏ
z y +ꝏ to − ꝏ θ 0 to π
P(r, θ, φ)
z +ꝏ to − ꝏ φ 0 to 2π

O y r OP
θ Angle of OP with z axis
φ Angle of (projection of OP in xy plane)
x
with x axis
z 0

x
x= rsinθcosφ
0 to 2π y= rsinθsinφ
y z= rcosθ

|ψ2| = probability density

|ψ2|dV = |ψ2| dxdydz
Volume element dxdydz = r2 sinθdrdθdφ
Laplacian operator

………(2)
 ………(3)

For 1 D

For 3 D

………(4)

………(5)
 ………(6)

Substitute the value of equation (2) in equation (6)

………(7)

Three independent equation in R, Θ, Φ

 ………(8)

Divide the equation (8) with RΘΦ and multiply by r2

………(9)

………(10)

Radial equation
 ………(11)

Θ dependent part and φ dependent part

Multiply equation (11) with sin2θ

………(12)

………(13)

Φ dependent equation
 By differentiating twice above equation

This equation is same as equation (13)

By applying condition of single valuedness, m is restricted to the values 0, ±1, ±2, ±3….
 ………(14)

Θ dependent equation

Principal quantuam number n = 1,2,3….(electron shell of an electron)

Azimuthal quantuam number l = 0, 1, 2……(n-1) (shape of atomic orbitals)

Magnetic quantum number m = 0, ±1, ±2 …. ±l (projection of orbital momentum

against specified axis )
 Solution of equation (14) is

Solution of equation (14) are called Associated Legendre polynomials

Solution of equation (10)

This equation can be manipulated to get it in the form of another equation

Of classical physics, the associated Laguerre equation. The solution of equation
(10) Which are everywhere finite, single valued, and have integrable squares
Exist only for the condition that

Where n = 1,2,3…
 0 ≤ l ≤ n−1

It means that energy of the electron in hydrogen atom or hydrogen like ion will
be restricted to the values

This is same expression as obtained by Bohr Theory

Θ Equation

is associated Legendre polynomial. θ can be calculated from here.

m = −l to +l , m = 2l+1
 l m value orbital Plm (cosθ) values N
value
0 0 s P00 (cosθ) = 1 1/√2
i.e. s doesnot depend
upon θ
1 0 p P01 (cosθ) = cosθ √3/2

1 ±1 p P±11 (cosθ) = sinθ √3/4

2 0 d P02 (cosθ) = 1/2(3cos2θ−1) √5/2

2 ±1 d P±12 (cosθ) = (3cosθsinθ) √5/12

2 ±2 d P±22 (cosθ) = (3sin2θ) √5/48

Spherical harmonics:
The product of eigen function of θ and Φ equation are called spherical harmonics.
Yl,m = Θ l,m (θ).Φm (φ)
l m orbital Yl,m (θφ)
0 0 s √1/4π

1 0 pz √3/4π cosθ

1 1 px √3/4π sinθcosφ

1 −1 py √3/4π sinθsinφ

2 0 dz 2 √5/16π (3cos2θ−1)
2 1 dxz √15/4π sinθcosθcosφ
2 −1 dyz √15/4π sinθcosθsinφ

2 2 dx2−y2 √15/16π sin2θcos2φ

2 −2 dxy √15/16π sin2θsin2φ
 n l m
1S ψ100 1 0 0 E1
2P Ψ211 2 1 1 E2

Ψ210 2 1 0 E2

Ψ21-1 2 1 -1 E2

2S Ψ200 2 0 0 E2

For any n, there will be n2 wave function and all are degenerate. n2 is degeneracy.
 p orbitals

l m
0 0 Y00 (θ,φ)= 1/√4π No angular
dependence
1 0 Y01(θ,φ)= √3/4π cosθ Independent
of φ
1 ±1 Y±11(θ,φ)= √3/8π sinθ e±iφ complex

for any m φ dependence will be e±imφ

 For d orbitals

l m
2 0 Y02 (θ,φ)= √5/16π (3cos2θ−1)
2 ±1 Y±12(θ,φ)= √3/4π sinθcosθe±iφ

2 ±2 Y±22(θ,φ)= √15/32π sin2θ e±2iφ