Physics and chemistry at the

nano-scale
NANOSCIENCE &TECHNOLOGY
102020705
Professional Elective

Kaushik Nath
Department of Chemical Engineering
G H Patel College of Engineering & Technology
 What happens at the nanoscale?

Why does size matter?

What is so special about nano-sized
materials?
How are their properties different from
those of conventional bulk materials?
Macroscopic properties.
Newtonian physics A different kind of small!
Quantum mechanics
 Physics at the nanoscale
Electromagnetic force: Due to smallness of
nanomaterials, their mass is extremely small and
gravitational forces become negligible. Instead
electromagnetic forces are dominant in
determining the behavior of atoms and
molecules

Wave-corpuscle duality of matter: For objects of

very small mass , such as electron, wave-like
nature has a more pronounced effect . Thus
electrons exhibit wave behavior and their
position is represented by a wave (probability)
function.
 Physics at the nanoscale

Tunneling: One of the consequences is a

phenomenon called tunneling. Tunneling is the
penetration of an electron into an energy region
that is classically forbidden
Classical physics states that a body can pass a
barrier (potential barrier) only if it has enough
energy to ‘jump’ over it. Therefore if the object
has lower energy that that needed to jump over
the energy barrier, the probability of finding the
object on the other side of the barrier is null.
In the quantum world the rules are
different!!
Quantum tunneling
Quantum Tunneling
 Physics at the nanoscale
Quantum confinement : In a nanomaterial, such as a
metal, electrons are confined in space rather than free
to move in the bulk of the material.
Quantization of energy : Electrons can only exist at
discrete energy levels. Quantum dots are nanomaterials
that display the effect of quantization of energy

Random molecular motion: At the macro scale this

motion is very small compared to the sizes of the
objects and thus it is not influential on how the object
moves. But at nanoscale these motions can be of same
scale as the size of the particles and thus have an
important influence on how they behave.
Increased surface to volume ratio
 Quantum confinemnet
Broadly quantum confinement is a restriction on the
motion of randomly moving electrons present in a material
to specific discrete energy levels rather than to quasi
continuum of energy bands. ... At such low dimensions the
electrons present in the material behave more or less
similar to the electrons present in atoms.
Quantum confinement causes the energy of the band gap to
increase . At very small dimensions , when the energy levels are
quantified, the band overlap present in metals disappears and is
actually transformed into a band gap.

This explains why some metals becomes semiconductors as

their size is decreased .
Quantum confinemnet
Quantum confinemnet
 Chemistry at the nanoscale
All types of bonds that are important in chemistry are equally important in
nanoscience.
Intra-molecular bonding: Ionic, covalent and metallic
Intermolecular bonding: ion-ion, ion-dipole interaction, van der Waals
interactions, H-bonds, hydrophobic interactions, repulsive forces (steric
repulsions)

Importance of surface atoms: Nanomaterials have a significant proportion

of atoms existing at the surface. This has a profound effect on reactions that
occur at the surface.

Surface energy: Atoms and molecules at the interface have enhanced

reactivity and a greater tendency to agglomerate ; surface atoms and
molecules are unstable , they have high surface energy .
 Intermolecular bonding

Hydrophobic effect : Property by which a non-polar molecule

tends to form aggregates of like molecules in water

Intramolecular bondings often hold together

macromolecules (such as proteins) in specific three
dimensional structure (quaternary structure) and leads to a
total loss of function (e.g. protein denaturation)
 Increase in surface area

A very simple example is granular sugar and caster sugar. Caster sugar is
finer , stickier (more surface adsorption) and dissolves faster in water
Increase in surface area
 Surface energy
Nanomaterials have a very large fraction of their atoms and
molecules on the surface , so surface energy is very high.

So, any system of high energy, will strive to attain a state of

lower energy, by whatever means possible.

Nanomaterials are inherently unstable , there they always tend

to minimize their inherent high surface energy.
One of the ways of reducing surface energy for nanoparticles
is agglomeration
Surface energy
Shape also matters
Catalysis
Example of gold as catalyst
 Electrical properties
There are three categories of materials based on their electrical
properties: (1) Conductors (2) semiconductors and (3) insulators

If an applied voltage exceeds band gap energy, electron jumps

from valence band to the conduction band, thereby forming
electron-hole pairs called excitons
 Why color is different?
The ‘colour’ of an object is the wavelengths of light that it reflects. This is
determined by the arrangement of electrons in the atoms of that substance
that will absorb and re-emit photons of particular energies according to
complicated quantum laws.
So tomatoes are red because the pigment atoms in the skin absorb
photons of all energies except those that correspond to red
wavelengths of light, which they reflect back to your eye.

As particle size increases, the wavelength of absorption

shifts towards longer, redder wavelengths. Red light is
then absorbed, and blue light is reflected, yielding
solutions with a pale blue or purple colour. As you
approach the bulk limit, the surface plasmon resonance
wavelengths move into the IR portion of the spectrum.
For other kinds of nanoparticles, for example, semi-conductor
nanoparticles, quantum confinement (e.g. quantum dots) might come into
play, and this affects the wavelength of absorption of electromagnetic
radiation, and hence the perceived colour.
 Interaction of light with matter

The color of a material is a function of the interaction between the light and the
object, if a material absorbs light of certain wavelengths, an observer will not see
these colors in the reflected light. Only reflected wavelengths reach our eyes and
this makes an object colorful.

Light incident on a material can be transmitted (T), absorbed (A) or reflected (R)
I = T + A +R

As the size of the materials is reduced scattering (S) of light can also contribute to
its color.

Reflection: when light strikes a smooth surface

Absorption: energy transformation
Transmission: the ability of light to pass through a material
Scattering: A phenomenon that occurs when radiation hits structure with
dimensions comparable to the incident wave length.