Quantum Mechanics

Basic Concepts of Classical and Quantum Mechanics

•A Little History on Mechanics
Classical or Newtonian mechanics appeared on the 17th century and
was very successful in describing the physics of the macroscopic
world. However, in the beginning of the 20th century, experiments
revealed a series of atomic and subatomic phenomena that could
not be explained by the old theory. This triggered the development
of Quantum mechanics.
•Main Principles of Classical Mechanics
In classical mechanics a system can be described by a number of dynamic
variables. The goal is to be able to calculate the exact values of these variables at
any given time and determine how these values evolve as a function of time t.
Once the position x(t) of a particle within an one-dimensional system is known,
a series of other variables such as the velocity ν(t), acceleration α(t), momentum
p(t), potential V and kinetic energy K can be calculated. Newton's Law is the basis
of classical mechanics:
F = mα or F = dp/dt
where F is the force acting on the particle and m the mass of the particle
• Classical mechanics (Newton's mechanics) and Maxwell's equations
(electromagnetics theory) can explain MACROSCOPIC phenomena such as motion of
billiard balls or rockets.
• Quantum mechanics is used to explain microscopic phenomena such as
photon-atom scattering and flow of the electrons in a semiconductor.
• In Newtonian mechanics, the laws are written in terms of PARTICLE TRAJECTORIES.
There are a few phenomenon’s which the classical mechanics failed to explain.
1. Stability of an atom
2. Spectral series of Hydrogen atom
3. Black body radiation
4. Heat capacity of solids
5. Compton effect
Quantum Mechanics: It is able to explain
1. Photo electric effect
2. Black body radiation
3. Compton effect
4. Emission of line spectra
5. Heat capacity of solids
The most outstanding development in modern science was the conception of
Quantum Mechanics in 1925. This new approach was highly successful in explaining
about the behavior of atoms, molecules and nuclei.
Main Principles of Quantum Mechanics
experimental observations led to the development of quantum theory. Given the new
theory, a system can now be described by a state function Ψ and not a set of dynamic
variables. This complicated wave function is the solution of Schrödinger's equation,
the equivalent to Newton's Law in classical mechanics.
The statistical nature of the state function indicates the probability of finding a particle
within a spatial range, in contrast to the Newtonian mechanics where a particle's
position can be accurately defined.
Quantum mechanics also accepts the quantization of energy, momentum, etc, when the
classical view can only accept a continuous range of values for each variable. In addition,
a particle in Quantum mechanics contains an amount of energy even at ground state.
This is due to the Heisenberg Uncertainty Principle, where the exact values of two
complimentary variables can never be measured simultaneously. The energy at ground
level for the classical mechanics is always zero.
Wave Particle Duality
Light can exhibit both kind of nature of waves and particles so the light shows
wave-particle dual nature. In some cases like interference, diffraction and polarization it
behaves as wave while in other cases like photoelectric and Compton Effect it behaves
as particles (photon).
De Broglie Waves
Not only the light but every materialistic particle such as electron, proton or even the heavier
object exhibits wave particle dual nature. De-Broglie proposed that a moving particle, whatever
its nature, has waves associated with it. These waves are called “matter waves”.
Energy of a photon is E = hv
For a particle, say photon of mass, m
E = mc2
mc2 = hv
mc2 = hc/ λ
λ = h/mc
Suppose a particle of mass, m is moving with velocity, v then the wavelength associated with it
can be given by
λ= h/mv or λ= h/p
(i) If v → 0, λ→∞ means that waves are associated with moving material particles only.
(ii) De-Broglie wave does not depend on whether the moving particle is charged or uncharged. It
means matter waves are not electromagnetic in nature.
 Heisenberg Uncertainty Principle

It is impossible to measure both the position and momentum simultaneously with

unlimited accuracy.
Δx. Δpx ≥ h / 4 π
Δx =uncertainty in position
Δpx = uncertainty in momentum (in the x-direction)

Then Δx Δp.͚ ≥ ħ /2 ( ħ= h/2π)

The product of Δx & Δpx of an object is greater than or equal to ħ /2.

•If we know the position (x) exactly, we know nothing about momentum (p x).
•If we know the momentum (px) exactly, we know nothing about position (x).
 Wave function (ψ):A wave function in quantum mechanics describes
the quantum state of an isolated system of one or more particles. There
is one wave function containing all the information about the entire system.
•In quantum Mechanics wave function (ψ) is a quantity associated with a moving
particle. It may be positive or negative sometimes it is a complex quantity (i.e., it
contains an imaginary number).

Thus if ψ = A+ iB; ψ * = A- iB

•Then ψ is the probability amplitude. Ψ has no physical significance; it has only

mathematical significance by itself. It is a mechanical function whose value
depends upon the coordinates of the electron in an atom ψ (x, y, z).
Probability density (ψ2)
The square of amplitude of an electron wave i.e. ψ2 at any point gives the
intensity of the electron wave at that point. Thus ψ2 is proportional to the
probability of finding a particle at a particular point at a particular time. It is the
probability density. It has physical significance
|ψ |2 = ψ .ψ * = A2 - i2B2 = A2 + B2
Always ψ 2 has real and positive value.
 3. Wavefunctions

• A particle trajectory is a classical concept.

• In Quantum Mechanics, a “particle” (e.g. an electron) does not follow a
definite trajectory {r(t),p(t)}, but rather it is best described as being
distributed through space like a wave.

• Wavefunction (ψ) – a wave representing the spatial distribution of a

“particle”.
• e.g. electrons in an atom are described by a wavefunction centred on the
nucleus.
• ψ is a function of the coordinates defining the position of the classical
particle:
– 1-D ψ(x)
– 3-D ψ(x,y,z) = ψ(r) = ψ(r,θ,φ) (e.g. atoms)
• ψ may be time dependent – e.g. ψ(x,y,z,t)
Properties of well behaved wave function
If the wave function satisfies below conditions then it is called well behaved
wave function.
1. It must be continuous and have a continuous first derivative everywhere
(fig- a,b).
∂ ψ/∂x, ∂ ψ/∂y, ∂ ψ/∂z must be continuous
2. It must be single valued (fig-c).
3. It must be finite everywhere (fig-d)..
4. It must be normalizable.
5.It cannot be zero everywhere.
Normalized wave function:
A wave function obtained on solving the S.W.E obeys this equation is said
to be normalized. so ʃ∞+∞ ψ .ψ* dτ =1
It is not possible that the wave function obtained always comes out to be
one. In that case the wave function multiplied by a constant (N) to give a
new wave function N ψ.
ʃ͚ -∞+∞ (Nψ) .(Nψ*) dτ =1
N2 ʃ͚ -∞+∞ (ψ). (ψ*) dτ =1
N= [1/ ʃ͚ -∞+∞ (ψ). (ψ*) dτ]1/2
N= normalization constant and Nψ is called normalized wave function
 Operator
• An operator is a mathematical instruction which acts on a
given function changes it into another function or the same
wave function multiplied by some constant real or complex.
• An operator is something that turns functions into
functions
• Example: The derivative operator,+,-,* etc
In quantum mechanics with every dynamical variable like

position, momentum , energy etc. there exists an operator.

Identifying the operators
Linear Operators
Almost all operators encountered in quantum mechanics are linear operators. A
linear operator is an operator which satisfies the following two conditions:

Commuting operators (Commutators):

Two operators commute if the following equation is true:

If the same answer is obtained subtracting the two functions will equal zero
and the two operators will commute.
Vector operator (∇):

Where I, j and k are unit vectors

Laplacain operator is a differential operator ,denoted by ∇2,

in cartesean coordinates:

in spherical polar coordinates

 Hermitian Operator
An operator A is said to be Hermitian, if it satisfies following
condition

Properties of Hermitian Operator:

❑ The Hermitian operator have real eigen values.
❑ Two Eigen functions of Hermitian Operator, belonging to
different eigen values are orthogonal.
Hamiltonian operator
In quantum mechanics, a Hamiltonian is an operator corresponding to the total energy of
the system in most of the cases. It is usually denoted by H, also Ĥ. It measures the total
energy of a system.
Total energy of particle: E = Kinetic Energy (KE) + Potential Energy (PE)

where E=T+V or
E or H = ½mv2 + V
= p2/2m + V (p = mv)
 Eigen functions and Eigenvalues
If an operator acts on a wave function and we get the same wave function
multiplied by some constant, then the wave function is known as eigen
function and constant is known as eigen value.

• This is an eigen value equation and can be rewritten as:

• (Operator)(function) = (constant factor)*(same function)

operator Q acting on function ψ multiplied

function ψ by a number Q
(eigen function) (eigenvalue)

(Note: ψ can’t be cancelled).

Examples: d/dx (eax) = a eax

d2/dx2 (sin ax) = −a2 sin ax

Problem-1

eikx is an eigen function of a operator

F(x) = eikx

Thus eikx is an eigen function

 Postulates of Quantum Mechanics
Postulate 1:

The state of a quantum mechanical system is completely specified by a wave

function ψ (r,t) that depends on the coordinates of the particles (r) and time t.
These functions are called wave functions or state functions. Wave function
contains all the information about a system.
Postulate 2:
wave function ψ (r,t) and its first and second derivatives are continuous, finite and
single valued of x also wave function ψ (r,t) is normalized ie.,

ʃ∞+∞ ψ .ψ* dτ =1
where ψ* - complex conjugate of ψ
Postulate 3:
A physically observable quantity can be represented by a linear, hermitian
operator.

An operator A is said to be Hermitian, if it satisfies following condition. Where ψ*

and ø are wave functions.
Postulate 4:
In any measurement of the observable associated with the operator, the only
values that will ever be observed are the Eigen values ‘a’ which satisfy the
Eigen value equation:

= operator
a = Eigen value
ψ = Eigen function

Postulate 5:

If ψ is not an Eigen function of then we talk of average values in

quantum mechanics. Mean value theorem is used to calculate the values
Expectation value in general:

Postulate 6:

The wave function of a system evolves in time in accordance with the

time dependent Schrodinger equation:
 PARTICLE IN 1-D BOX
(MOTION OF AN ELECTRON IN ONE DIMENSIONAL POTENTIAL WELL)
Consider an electron of mass m, moving along positive x-axis between two walls
of infinite height, one located at x=0 and another at x=a. Let potential energy of
the electron is assumed to be zero in the region in-between the two walls and
infinity in the region beyond the walls.

V=∞ V=0 V=∞

X=0 X=L

X-axis 27
Case-1:Out side the box V= ∞ :
The Schrodinger’s wave equation representing the motion of the particle in the
region beyond the two walls is given by

The only possible solution for the above equation is ψ=0.

Since ψ=0 , the probability of finding the particle in the region x<0 and x>a is Zero .
i.e., particle cannot be found in region beyond the walls.

Case-2:Inside the box V=0:

The Schrodinger’s wave equation representing the motion of the particle
in the region between the two walls is given by

28
 Solution of the equation 1 is of the form

Where A and B are unknown constants to be determined.

29
The equations are called boundary conditions. Using the I boundary condition in
equation 2, we get

Therefore equation 2 becomes

Using condition II in equation 3 we get

30
Therefore correct solution of the equation 1 can be written as

A is a constant its value obtanied from normalization process

Normalization of wave function:

We know that particle is definitely found somewhere in space

Therefore Normalized wave function is given by

On simplifying the above equation , we get A=

Substitute A value in equation -4 We get

The above equation represents Eigen wave functions 31

 Where n=1,2,3,..
(n=0 is not acceptable because, for n=o the wave function ψ becomes zero for all values
of x. Then particle cannot be found anywhere)
Substituting for K in equation 1a we get

Therefore energy Eigen values are represented by the equation

Where n=1,2,3,..
It is clear from the above equation that particle can have only desecrated values of
energies. The lowest energy that particle can have corresponds to n=o , and is called
zero-point energy. It is given by

32
Similarly for n=1

0 0 0

L 0 0

33
 Similarly for n=2

0 0 0

0 0

L 0 0
Wavefunctions, probability density and energies are as shown in the
figure.

35
Wave functions for the particle in a box
ψ(x) = 0
Example -1: What is the probability of finding an electron in a box of length 2 Ao in the
middle of the box in an interval of length 0.1 Ao . This probability may be represented
as P ( 0.95Ao x 1.05Ao)
Solution:
A simple and approximate way of calculating this probability is to use the square of the
wave function at the midpoint of the box and multiply it by the interval 0.1Ao
| Ψ (x = 1 ) | 2 .dx = (2 / 2) 1/ 2 sin (1 . ½ ) 0.1 = 0.1

A precise way of calculating this probability is to integrate the square of the wave
function from 0.95 Ao to 1.05 Ao. This is necessary because the wave function is not
constant over this interval (as was assumed in the above approximate calculation).
a ∫b ( 2 / L) sin 2 (n x / L )dx = ½ a ∫b [ 1- cos (2 nx / L )]dx
= (b - a ) / L – (1/ 2 n) sin ( 2 nx / L) |ab
In our problem L = 2 , b = 1.05 , a = 0.95 and n = 1
P ( 0.95 x 1.05 ) = (1.05 – 0.95) / 2 – (1/ 2 ) [ -0.1544 – 0.1564]
= 0.05 + 0.0498
= 0.0998
In the present case, the approximate calculation is good since the wave function is not
varying very much in this interval. When the wave function changes rapidly, the
approximate method will not give good results.
A40.1

The first five wave functions for a

particle in a box are shown. The
probability of finding the particle near
x = L/2 is

A. least for n = 1.
B. least for n = 2 and n = 4.
C. least for n = 5.
D. the same (and nonzero) for n = 1, 2, 3,
4, and 5.
E. zero for n = 1, 2, 3, 4, and 5.
Q40.2

Compare n=1 and n=5 states. The average

value of the x-component of momentum is

A. least for n = 1.
B. least for n = 5.
C. the same (and nonzero) for n = 1
and n = 5.
D. zero for both n = 1 and n = 5.
A40.2

Compare n=1 and n=5 states. The average

value of the x-component of momentum is

A. least for n = 1.
B. least for n = 5.
C. the same (and nonzero) for n = 1
and n = 5.
D. zero for both n = 1 and n = 5.

The wave functions for the particle in a box are superpositions of waves propagating
in opposite directions. One wave has px in one direction, the other has px in the
other direction, averaging to zero.
Q40.3

The first five wave functions for a

particle in a box are shown.
Compared to the n = 1 wave function,
the n = 5 wave function has

A. the same kinetic energy (KE).

B. 5 times more KE.
C. 25 times more KE.
D. 125 times more KE.
E. none of the above
A40.3

The first five wave functions for a

particle in a box are shown.
Compared to the n = 1 wave function,
the n = 5 wave function has

A. the same kinetic energy (KE).

B. 5 times more KE.
C. 25 times more KE.
D. 125 times more KE.
E. none of the above
Spherical Polar coordinates
Comparison of Equations for Linear and Circular Motion

Linear Motion
Circular Motion

Moment of inertia
Mass m
Velocity Angular velocity
v

Momentum Angular momentum

p=mv
Energy Energy

Or
 Operators in other coordinates
Kinetic energy in spherical coordinates:

Angular momentum operators in spherical coordinates:

 RIGID ROTOR
or
Diatomic Molecule As A Rigid
Rotator
The rotation of a diatomic molecule can
be considered by a rigid rotator.
Consider a diatomic molecule with a
rigid bond length, ie., whose bond
length does not change during motion.

Thus the diatomic molecule is

equivalent to a single point mass μ at a
fixed distance r from the axis of
rotation. Such a system is called a rigid
rotator.
(V=0)
 Rigid Rotator consists of two point masses m1 and m2 which separated by a
fixed distance r. The distance of m1 from the centre of mass is r1 and distance
of m2 fro centre of mass is r2.

By the definition of Centre of mass, we have

m 1r 1 = m 2r 2
r1 + r 2 = r

Now, the moment of inertia of the molecule about the axis of rotation is given by
I= m1r12+m2r22
m 1m 2
m 1 m 2 r2
m1m2
But is the reduced mass µ of the molecule. Then
m1 m2
I = µr2
14
 The inter atomic distance does not change during rotation ie., bond length Is fixed.
So its PE is constant ie., V=0. It total energy is the KE only.
Total energy= PE+KE

E or
Schrödinger equation is:

(V=o)

---------1

Where H (or) L=Iω2/2 = L2/2I

ω= v/r (Angular velocity)

L = Iω → angular momentum
Angular momentum operators in spherical coordinates:

------2

Substitute equation 2 in equation then 1Schrodinger equation is

terms only contain θ terms only contain

φ
The wavefunction must be a product of the independent functions:

equation is

-----3

----4
equation is

Solution to (4) is simple, same form as for free electron:

Where ml = magnetic QN
Solution of equation (3)

Associated Legendre Polynomial

or

l= Azimuthal Quantum No J= Rotational Quantum No

(x)

Where (x)= cos

Combined solution with normalization are called spherical harmonics:
SWE is

where:

These are also referred to by the variable

then
Zero Point Energy

E =0
rot0

→ There is no zero point energy associated with rotation!

 J level Energy
J=6 42B

J=5 30B

J=4 20B
J=3 12B
J=2 6B
J=1 2B
J=0 0B

Energy of rotational energy levels: (Not equally spaced)

1. When an H2 molecule is chemisorbed on a crystalline surface, its rotation can be
approximated as that of a 2D rigid rotor. The H2 bond length is 0.74 Å Calculate the
frequency (in cm-1) of the lowest energy rotational transition of chemisorbed H2.

r = 0.74 Å = 0.74x10-10 m
1 amu = 1.66x10-27 kg
ħ = 1.05x10-34 J•s h = 6.63x10-34 J•s
c = 3.00x1010 cm/s

m2 = 1

m1 = 0
Molecular Orbital Theory
Molecular orbital theory (MOT) or Linear Combination of Atomic
Orbital’s (LCAO Theory):
In 1927 hietler and london proposed the valance Bond theory .Valence Bond Theory
fails to answer certain questions like Why He2 molecule does not exist and why O2 is
paramagnetic? It does not explain the variations of magnetic moment with
temperature. It does not take into account the splitting of d –energy levels. It does not
predict the relative stabilities of different structures.
Therefore in 1932 F. Hood and Robert S. Mulliken came up with theory known as
Molecular Orbital Theory to explain questions like above. According to Molecular
Orbital Theory individual atomic orbital’s combine to form molecular orbital’s, as the
electrons of an atom are present in various atomic orbital’s and are associated with
several nuclei.
Molecular orbital (MO) theory is a more sophisticated quantum mechanical model of
bonding in molecules that can be applied successfully to both simple and complex
molecules.
Salient Features of Molecular orbital theory (MOT):
1. As the combining atoms approach each other their atomic orbital’s with same or
nearly same energy and appropriate symmetry undergo linear combination to form a
completely new set of orbital’s known as molecular orbitals.
2. The number of molecular orbitals formed is equal to the number of atomic orbitals
participated in the linear combination.
When two atoms are combine to form a molecule then Each atoms of atomic orbital
combine to form molecular orbital, Molecular orbital’s are classified on the basis of
energy,
a) Bonding Orbital: The orbital having lowest energy is called Bonding Orbital
When addition of wave function takes place, the type of molecular orbital’s formed are
called Bonding Molecular orbital’s and is represented by ΨMO = ΨA + ΨB.
It is similar to constructive interference occurring in phase because of which
electron probability density increases resulting in formation of bonding orbital.
b) Anti Bonding Orbital: The orbital having high energy is called Anti
Bonding orbital. When molecular orbital is formed by subtraction of wave
function, the type of molecular orbital’s formed are called Anti bonding
Molecular Orbital’s and is represented by ΨMO = ΨA - ΨB.
It is similar to destructive interference occurring out of phase resulting in formation of
anti bonding orbitals.
It is represented by s* (*) is used to represent anti bonding molecular orbital called
Sigma Anti bonding.
3. BMO has lower energy and hence greater stability than ABMO. First BMO
are filled then ABMO starts filling because BMO has lower energy than that
of ABMO.
4. Unlike atomic orbitals, molecular orbitals are polycentric.
5. Shape of molecular orbitals depends upon the shape of atomic orbitals from
which they are generated.
6. Filling of follows the same rules used for filling of atomic orbital’s
a. Aufbau Principle,
b. Pauli’s Exclusion Principle,
c. Hund’s Rule
The relative energies of MOs in increasing order have been found to be as follows
•For H2 to N2: σ1s <σ1s* <σ2s<σ 2s*< [π2px= π2py] <σ2pz< [π*2px= π*2py] <σ*2pz
•For O2 to Ne2: σ1s <σ1s*<σ2s<σ 2s*<σ2pz<[π2px=π2py] < [π*2px= π*2py]<σ*2pz
Bond Order: It may be defined as the half of difference between the number of
electrons present in the bonding orbital’s and the anti bonding orbital’s that is,
Bond order (B.O.) = (No. of electrons in BMO - No. of electrons in ABMO)/ 2.
Bond order (B.O.) = (Nb - Na)/ 2
Those with positive bonding order are considered stable molecule while those with
negative bond order or zero bond order are unstable molecule.
Magnetic Behavior: If all the molecular orbital’s in species are spin paired, the
substance is diamagnetic. But if one or more molecular orbital’s are singly occupied it
is paramagnetic. For Example, if we look at CO Molecule, it is diamagnetic as all the
electron in CO are paired.
Homo Nuclear Diatomic Molecules:
1. Molecular orbital diagram for the H2 molecule
Each H-atom has one electron and therefore 2 electrons in H2 molecule. These electrons
are added to the diagram in the figure below, one at a time, starting with the lowest
energy molecular orbital.
Molecular orbital electronic configuration of H2 molecule =(σ1s)2
H2 molecule is Diamagnetic
2. Molecular orbital diagram for the O2 molecule.
There are six valence electrons on a neutral oxygen atom and therefore 12 valence
electrons in an O2 molecule. These electrons are added to the diagram in the figure
below, one at a time, starting with the lowest energy molecular orbital.
Molecular orbital electron configuration of O2:
(σ1s)2(σ1s*)2(σ2s)2(σ2s*)2(σ2pz)2[π2px= π2py]4 [π*2px= π*2py]2
Bond order (B.O.) = (Nb - Na)/ 2 = 8-4/2 = 2
O2 molecule has 2 unpaired electrons so it is Paramagnetic in nature.
Hetero nuclear diatomic molecules
1.Molecular orbital diagram for the CO molecule:
• CO molecule has 14 electrons
• sp mixing occurs
• (σ2pz) orbital has more energy than [π2px= π2py]
• Because of higher electro negativity of oxygen, its atomic orbitals would be of lower
energy than the corresponding atomic orbitals of carbon .
• Molecular orbital electron configuration of CO:
(σ1s)2(σ1s*)2(σ2s)2(σ2s*)2 [π2px= π2py]4 (σ2pz)2
• Bond order (B.O.) = (Nb - Na)/ 2 = 8-2/2 = 3
• CO molecule is Diamagnetic in nature because all the electrons are paired.

Properties: Stable, exist, diamagnetic, low spin and colorless

 Molecular Orbital diagram of Carbon Monoxide
(σ*2pz)

2p
[π*2px= π*2py]

2 px 2 py 2 pz
σ2pz)2
2p
2 px 2 py 2 pz

[π2px= π2py]4
2s
(σ2s*)2

C-atomic orbital (σ1s)2 2s

CO- molecular orbital O-atomic orbital

2.Molecular orbital diagram for the NO molecule:
• NO molecule has 15 electrons
• sp mixing not occurs
• (σ2pz) orbital has less energy than [π2px= π2py]
•Because of higher electro negativity of oxygen, its atomic orbitals would be of lower
energy than the corresponding atomic orbitals of nitrogen .
• Molecular orbital electron configuration of NO:
(σ1s)2(σ1s*)2(σ2s)2(σ2s*)2 (σ2pz)2 [π2px= π2py]4 [π2px= π2py]1
Bond order (B.O.) = (Nb - Na)/ 2
= 8-3/2 = 2.5
NO molecule is paramagnetic in nature.
Properties: Stable, exist, paramagnetic, high spin and colored