Atomic structure

Electrons are tiny particles. Thus they follow the rules of something
called Quantum Physics, the branch of Physics that explains the world
of the very small. The basic rules of Quantum world that we would be
interested in are:

• Wave-particle duality
• Heisenberg’s Uncertainty principle
• Energy levels are discrete – electrons absorb and emit energy in
“packets” to leap from one energy level to another.
 Do electrons move around the nucleus in fixed paths?

• All particles exhibit something called wave-particle duality i.e. properties of both particle and wave. For
large particles, the wavelength is very very short compared to the dimensions of the particle, so the wave
properties do not manifest themselves for large particles. However, for a tiny particle (example - an
electron) the wavelength is comparable to the dimension of the electron and the wave property is
prominent.

• For a tiny particle like an electron, it is impossible to measure both its position and velocity accurately at a
given instant (famously captured in something called Heisenberg’s Uncertainty Principle). It behaves more
as a blur than as a definite particle. We can thus never determine the exact past/present/future position
of an electron, but only predict the probability of finding an electron at a location.

• Thus it is wrong to think of an electron as a particle moving along a fixed trajectory

or orbit. Rather, we can think of an electron as a blur or cloud of negative charge
smeared over space, with certain 3D regions having the highest charge
densities.

• Or, if we prefer to think of electron as a particle instead of a cloud, then it is a very

tiny particle moving around fuzzily around the nucleus and there are certain 3D
regions where the probability of finding the electron is the highest.
 Why does the negatively charged electron buzz around at
some distance away from the positively charged nucleus?
Why does it not fall on the nucleus?
• A body always seeks out its most energetically stable state where the sum of its total energy
content is minimum

• As an electron is moved away from the nucleus, work is being done ON it against the nuclear force
of attraction. So, potential energy of an electron increases with increase in distance from nucleus.,

• As an electron moves towards the nucleus, it accelerates due to the nuclear pull (electromagnetic
force of attraction) and its velocity increases So, kinetic energy of an electron increases with
decrease in distance from nucleus, the k.e. of the electron becoming infinitely high when it is
right on the nucleus.

• So, the most energetically stable position of the electron is neither on the nucleus nor very far
away from the nucleus, but within a region which is a certain “happy distance” away from the
nucleus and is associated with the minimum possible total energy content. This region is called
an energy shell.
Why are all the electrons not “lumped” together in one “happy”
region/energy shell? Why are the electrons spread out in different shells?

• Electrons repel each other so they minimize this

repulsive force by “spreading out” in different regions
or energy shells.

• The energy shell closest to the nucleus has the least

total energy content; the energy content increases as
distance from nucleus increases.
Energy shells are discrete and not continuous
•Each electron has its own ground state or energetically most stable state. But it can absorb
energy supplied from outside and get “excited” to a higher energy state i.e, leap to a higher
energy region further away from the nucleus. Eventually, the electron falls back to a lower
energy region by releasing an amount of energy equal to the difference between the energy
of two energy regions.

•Energy emitted is associated with frequency (higher frequency for higher energy)

•Scientists performed experiments of exciting atoms of different elements with energy. The
electrons of the atoms absorbed energy, got excited to higher energy level and then fell
back to lower energy levels by emitting energy. Scientists passed the emitted energy
through prism/diffraction gratiing. They studied the frequency of the energy waves and
noticed two things:
Emission spectrum – discrete lines
• instead of a continuous energy band which would have suggested a continuous “roll-
down” of electrons from higher to lower energy, there were separate lines of different
frequencies. This suggested to the scientists that the energy shells are not like one
continuous rolling field where the electrons can spread out and “graze” but rather discrete
regions or quantum shells, separated by “energetically improbable regions” where the
electrons cannot move about. Electrons absorb and emit energy in discrete packets to
“leap” from one energy shell to another. Continuous spectrum

•Each element has its own unique pattern or fingerprint of emission lines or “emission
spectrum”. In fact, to this day, the energy emitted by distant stars are passed through
diffraction grating and the emission spectra is used to identify the elements present in the
star.
Subshells
• Scientists later found that each energy region/shell is actually not
one single region but several subregions or subshells with very
close but slightly different energy contents.

• the first quantum shell has only 1 subshell - 1s

• the second quantum shell has two subshells – 2s and 2p
• the third quantum shell has three subshells – 3s, 3p and 3d
• the fourth quantum shell has three subshells – 4s, 4p, 4d and 4f
• the fifth quantum shell has three subshells – 5s, 5p, 5d, 5f and 5g
 Orbitals
• Each subshell consists of orbitals. An orbital is a 3D region around a nucleus which can
hold upto 2 electrons with opposite spins. The probability of finding an electron within
an orbital is as high as 90%.

• Suppose you had a single hydrogen atom and at a particular instant plotted the
position of the one electron. Soon afterwards, you do the same thing, and find
that it is in a new position. You have no idea how it got from the first place to the
second. You keep on plotting the positions over and over again, and gradually
build up a sort of 3D map of the places that the electron is likely to be found. In
the hydrogen case, the electron can be found anywhere within a spherical space
surrounding the nucleus. The diagram shows a cross-section through this
spherical space.
• So, we may say that 90% off the time an electron will be found within a fairly
easily defined region of space quite close to the nucleus. Such a region of space
is called an orbital. You can think of an orbital as being the 3D region of space in
which the electron lives or the 3D region traced out by an electron over time.

• The s subdhell has 1 orbital and can house 1×2 or 2 electrons.

• The p subdhell has 3 orbitals and can house 3×2 or 6 electrons.
• The d subshell has 5 orbitals and can house 5x2 or 10 electrons.
• The f subshell has 3 orbitals and can house 7x2 or 14 electrons.
• ....
Subshells and orbitals
It helps to mentally think of shells as buildings, subshells as floors in the building, and orbitals as double-occupancy flats in a floor:
• The shell (building) closest to the nucleus (park) is energetically most stable (most desired building) and but as we move to elements
with larger atomic number (more electrons), the electrons must spread out across buildings further away (higher energy shells)

• Within a building, the bottom-most floor has the least energy; energy content increases as one moves to higher floors. So, the floors
get filled up from bottom to top i.e., from the lowest energy subshell (s subshell) to higher energy subshells (p, d, f...)

• Within a floor, all the rooms (orbitals) are identical except for their orientation in space.

• Within a room (orbital), there can be 1 electron or 2 spin-paired (opposite spins) electrons. All the orbitals (rooms) in a subshell
(floor) fill up singly first before spin-pairing within an orbital. (Hund’s Rule).
Size and shapes of the orbitals
s orbitals

Cross-sectional view of
electron density map of
1s and 2s orbitals
 Cross-sectional
view of electron
p orbitals – 3D view density map of a p
orbital
d orbitals – 3D view
 Representing electronic configuration
(particles-in-box representation and superscript
representation)
Electrons in a box representation
One more example – sodium (Na)
Periodic Table
 Electronic configurations
• Hund’s rule

• Quantum numbers -Pauli’s exclusion principle

• Electron density map

• Electrons getting pushed from 3d to 4s because energy gap between 3d and 4s is very less yet 4s is more
spacious and hence less electrons experience less repulsion there –

• Using Auf Bau Principle as a tool for working out electronic configuration quickly
• exception of Cr and Cu (3d5 4s1 is energetically more stable than 3d4 4s2; 3d10 4s1 is more
energetically stable than 3d94s2)

• Students need to be able to do any configuration from H to Kr

• s p d f blocks in the Periodic Table

• 4s electrons get lost first when transition metals lose electrons

Atomic orbitals of Na atom
 Ionization Energy/Potential
• Why study this subtopic?
• 1st IE (definition and concept)
• 2nd IE (definition and concept)
• Successive IE - working out the number of electrons in each shell,the evidence of
quantum shells
• Logarithmic scale
• Factors affecting IE values - nuclear charge, orbital distance, repulsion (shielding)
effect of other electrons
• Trend of IE down the group (decreasing trend since last 2 facts override the first
factor)
• Trend of IE across the period – general trend and exceptions
3 Factors affecting Ionization Energy
• Nuclear charge (number of protons) : more the nuclear charge, more
nuclear pull on the electron, less the energy of the electron

• Distance of the orbital: further away from the nucleus is the orbital,
more the energy of the electron

• Repulsion (shielding) effect of other electrons: More the number of

neighboring electrons, more the electron-electron shielding effect,
more is the energy of the electron
- Successive ionization energies of an element
- Successive ionization energies of an element – why logarithmic scale?
- Sharp jump in ionization value when “breaking” into an inner quantun shell

- Steady or gentle rise in I.E. Values within a shell as electron- electron repulsion decreases
 Trend of 1st I.E. Values down a group
• The second 2 factors (distance and shielding) override the effect of the first factor
(increased nuclear charge). So, effective nuclear pull deceases. So, I.E. values
deceases down the group.
 General Trend of 1st I.E. values across a
period
• General trend: As we move across a period, the outer most electron(s) are getting added in the same
shell and hence roughly at around same distance away from the nucleus. The repulsion (shielding)
effect from outer electrons increases as the number of electrons increases. However, the effect of
increasing nuclear charge across the period way dominates over any effect of the other two factors.
This means an increased effective nuclear pull and hence more I.E.
These dips are
evidences of
quantum
subshells
Periodicity

Metallic charachter
Atomic radIi
IE
Melting point boiling point - bonding
Atomic radii
Trend in melting and boiling points
Periodic Table - Modified