Electronic Structure

of Atoms
What happens when you turn on a neon light?

Electrons in neon atoms, excited to a higher energy level by

electricity, emit light when they drop back down to a lower energy.

This is explained by quantum theory

Which describes the behavior of electrons in atoms.

Our current understanding of electronic structure of atoms has come

from analysis of light either emitted or absorbed by substances.
Visible light is electromagnetic radiation.

Since Electromagnetic radiation carries energy through space it is called

radiant energy.

There are many types of electromagnetic radiation in addition to visible

light.

All electromagnetic radiation share one thing.

They all travel at a speed of 3.00 x 10 8m/s.

The speed of light.

Waves

To understand the electronic structure of atoms, one must

understand the nature of electromagnetic radiation.

The distance between corresponding points on adjacent waves is the

wavelength (λ).

Different forms of electromagnetic radiation have different

properties due to different wavelengths.
Waves
The number of waves passing a given
point per unit of time is the frequency
(ν).

For waves traveling at the same

velocity, the longer the wavelength,
the smaller the frequency.
 Electromagnetic Radiation

All electromagnetic radiation

travels at the same velocity: the
speed of light (c), 3.00  108 m/s.

Therefore,

c = λν
Light can be explained as having wave-like properties, but the wave
model does not explain several phenomena.
The emission of light from hot objects

Blackbody radiation

Emission of electrons from metal surfaces on which light shines

Photoelectric effect

Emission of light from electronically excited gas atoms

Emission Spectra
The Nature of Energy

The wave nature of light does not

explain how an object can glow
when its temperature increases.

Max Planck explained it by

assuming that energy comes in
packets called quanta.
Hot objects and the Quantization of Energy
When solids are heated they emit radiation.

Red hot iron, Tungsten filament in bulb glows white.

What is the relationship between temperature and the intensity and the
wavelengths of the emitted radiation?

In 1900 Max Plank solved the problem by making an assumption:

Energy can be either released or absorbed by atoms only in discrete “chunks” of some
minimum size.

Plank gave the name quantum, meaning fixed amount, to the samllest quantity of energy that
can be emitted or absorbed as electromagnetic radiation.

He proposed that the energy, E, of a single quantum equals a constant times the frequency of
the radiation

E=hv
E=hv
h = 6.626 x 10-34 Js

Matter is allowed to emit and absorb energy in whole number

multiples of hv.

hv,2hv,3hv, etc.

If the quantity of energy emitted is 3hv, we say that 3 quanta of energy

has been emitted.

Because the energy can only be emitted in specific amounts we say

the energy is quantized.

Think of a ramp vs. a staircase.

 The Nature of Energy

Einstein used this assumption to explain

the photoelectric effect.

He concluded that energy is

proportional to frequency:

E = hν

where h is Planck’s constant, 6.63 

10−34 J-s.
Einstein used Plank’s theory to explain the photoelectric effect.

Light shining on a clean metal surface causes the surface to emit electrons

For each metal there is a minimum frequency below which there are no
electrons emitted.

Ex. Light with a frequency of 4.6 X 1014/s or greater will cause cesium to
emit electrons
Einstein assumed that the radiant energy striking the metal surface is
behaving not like a wave but rather as if it were a stream of tiny energy
packets.

He called each energy packet a photon.

 The Nature of Energy

Therefore, if one knows the wavelength

of light, one can calculate the energy in
one photon, or packet, of that light:

c = λν

E = hν
The Nature of Energy

Another mystery involved the

emission spectra observed from
energy emitted by atoms and
molecules.
The Nature of Energy

One does not observe a continuous

spectrum, as one gets from a white
light source.

Only a line spectrum of discrete

wavelengths is observed.
Not all radiant sources produce a continuous spectrum

Using CRT’s with various gases, they each emit different colors of light

When this light is passed through a prism only a few wavelengths are
present

A spectrum containing radiation of only specific wavelengths is called line

spectrum.
When scientists first detected the line spectrum of hydrogen, they
were fascinated by its simplicity.

Only 4 lines were detected in the visible portion of the spectrum

Johan Balmer showed that the wavelengths of these four visible

lines of hydrogen fit a simple formula
 1 - 1
1/λ= RH (n 2 n 2 )
i f

Soon Balmer’s equation was extended to a more general one, called

Rydberg equation

where RH is the Rydberg constant, -1.096776 x 107m-1,

and ni and nf are positive integers representing the initial
and final energy levels of the electron.
Bohr’s Model
After Rutherford discovered the nuclear nature of the atom scientists
thought of the atom as a microscopic solar system in which the electrons
orbited the nucleus

So Bohr then started by assuming that the electrons move in circular orbits
around the nucleus.

According to classical physics, an electrically charged particle that moves in

a circular path should continuously lose energy by emitting electromagnetic
radiation and spiral into the nucleus.
Does this happen?

Of course not, hydrogen atoms are stable.

How is it that hydrogen seems to violate these laws?

Bohr approached the problem in the same way Plank did.

Prevailing laws of physics were inadequate in explaining atoms!

He adopted Plank’s idea that energies are quantized.

Bohr based his model on three postulated

Only orbits of certain radii, corresponding to certain definite

energies, are permitted for the electron in a hydrogen atom.

An electron in a permitted orbit has a specific energy and is in an

allowed energy state. An electron in an allowed energy state will
not radiate energy and therefore will not spiral into the nucleus.

Energy emitted or absorbed by the electron only as the electron

changes from one allowed energy state to another. This energy is
emitted or absorbed as a photon, E = hν
The Nature of Energy

 Niels Bohr adopted Planck’s assumption

and explained these phenomena in this
way:

1. Electrons in an atom can only occupy certain

orbits (corresponding to certain energies).
The Nature of Energy

 Niels Bohr adopted Planck’s assumption

and explained these phenomena in this
way:

2. Electrons in permitted orbits have specific,

“allowed” energies; these energies will not be
radiated from the atom.
 The Nature of Energy

 Niels Bohr adopted Planck’s assumption

and explained these phenomena in this
way:

3. Energy is only absorbed or emitted in such a

way as to move an electron from one “allowed”
energy state to another; the energy is defined by

E = hν
The Nature of Energy
1 - 1
λ = R ( 2 2 )
ni nf

The energy absorbed or emitted from the process

of electron promotion or demotion can be
calculated by the equation:

where R is the Rydberg constant, 109737.31/cm,

and ni and nf are the initial and final energy levels
of the electron.
Bohr calculated the energies corresponding to each allowed orbit for the
electron in the hydrogen atom

E= (-hcR/n2)

The integer n can have values fro 1 to infinity and is called the principle
quantum number

Each orbit corresponds to a different value for n

The radius of the orbit increases as n increases

The energies are negative for all values of n.

The lower (more negative) the energy is, the more stable the atom will be.

The energy is lowest for n=1

As n gets larger it becomes successively less negative

n=1, the lowest energy state, is the ground state.

When electrons are in higher energy states they are in the excited state.
What happens to the radius and the energy as n becomes infinitely large?

Radius increases and electron is separated from the nucleus.

Energy=0.

Bohr postulated that electrons could jump from one energy state to another
by absorbing or emitting photons whose radiant energy corresponds exactly
to the energy difference between the two states.
The Wave Nature of Matter

Louis de Broglie posited that if light can have material properties, matter
should exhibit wave properties.

He demonstrated that the relationship between mass and wavelength was

h
λ = mv
Suppose an electron orbiting the nucleus could be thought of not as particles
but rather as a wave, with a characteristic wavelength.

He said that the wavelength of the electron depends on its mass and its
velocity.

mv is momentum

Therefore any object would give rise to a characteristic matter wave.

Objects with large mass have meaningless wavelengths, but not very small
objects.
What is the wavelength of an electron moving with a speed of
5.97 X 106m/s? Mass of an electron is 9.11 x 10-28g

.122nm
The Uncertainty Principle

Heisenberg showed that the more precisely the momentum of a particle is

known, the less precisely is its position known:

h
(Δx) (Δmv) ≥
4π

In many cases, our uncertainty of the whereabouts of an electron is greater

than the size of the atom itself!
Quantum Mechanics

Erwin Schrödinger developed a

mathematical treatment into which
both the wave and particle nature of
matter could be incorporated.

It is known as quantum mechanics.

Quantum Mechanics

The wave equation is designated with a

lower case Greek psi (ψ).

The square of the wave equation, ψ2, gives

a probability density map of where an
electron has a certain statistical likelihood
of being at any given instant in time.
Quantum Numbers

Solving the wave equation gives a set of wave functions, or orbitals, and
their corresponding energies.

Each orbital describes a spatial distribution of electron density.

An orbital is described by a set of three quantum numbers.

Principal Quantum Number, n

The principal quantum number, n, describes the energy level on which the
orbital resides.

The values of n are integers > 0.

Azimuthal Quantum Number, l

This quantum number defines the shape of the orbital.

Allowed values of l are integers ranging from 0 to n − 1.

We use letter designations to communicate the different values of l and,

therefore, the shapes and types of orbitals.
Azimuthal Quantum Number, l

Value of l 0 1 2 3
Type of orbital s p d f
Magnetic Quantum Number, ml

Describes the three-dimensional orientation of the orbital.

Values are integers ranging from -l to l:

−l ≤ ml ≤ l.

• Therefore, on any given energy level, there can be up to 1 s orbital, 3 p

orbitals, 5 d orbitals, 7 f orbitals, etc.
Magnetic Quantum Number, ml

Orbitals with the same value of n form a shell.

Different orbital types within a shell are subshells.

s Orbitals

Value of l = 0.

Spherical in shape.

Radius of sphere increases with

increasing value of n.
s Orbitals

Observing a graph of probabilities

of finding an electron versus
distance from the nucleus, we see
that s orbitals possess n−1 nodes, or
regions where there is 0 probability
of finding an electron.
p Orbitals

Value of l = 1.

Have two lobes with a node between them.

d Orbitals

Value of l is 2.

Four of the five

orbitals have 4 lobes;
the other resembles a p
orbital with a doughnut
around the center.
Energies of Orbitals

For a one-electron hydrogen

atom, orbitals on the same
energy level have the same
energy.

That is, they are degenerate.

Energies of Orbitals

As the number of electrons

increases, though, so does the
repulsion between them.

Therefore, in many-electron
atoms, orbitals on the same energy
level are no longer degenerate.
Spin Quantum Number, ms

In the 1920s, it was discovered that

two electrons in the same orbital do
not have exactly the same energy.

The “spin” of an electron describes its

magnetic field, which affects its
energy.
Spin Quantum Number, ms

This led to a fourth quantum number,

the spin quantum number, ms.

The spin quantum number has only 2

allowed values: +1/2 and −1/2.
Pauli Exclusion Principle

No two electrons in the same atom

can have exactly the same energy.

For example, no two electrons in the

same atom can have identical sets of
quantum numbers.
Electron Configurations

Distribution of all electrons in an

atom

Consist of

Number denoting the energy level

Electron Configurations

Distribution of all electrons in an

atom

Consist of

Number denoting the energy level

Letter denoting the type of orbital

Electron Configurations
Distribution of all electrons in an
atom.

Consist of

Number denoting the energy level.

Letter denoting the type of orbital.

Superscript denoting the number of

electrons in those orbitals.
Orbital Diagrams

Each box represents one orbital.

Half-arrows represent the electrons.

The direction of the arrow

represents the spin of the electron.
Hund’s Rule

“For degenerate orbitals, the

lowest energy is attained when
the number of electrons with
the same spin is maximized.”
Periodic Table

We fill orbitals in increasing

order of energy.

Different blocks on the periodic

table, then correspond to
different types of orbitals.
Some Anomalies

Some irregularities occur

when there are enough
electrons to half-fill s and
d orbitals on a given row.
Some Anomalies

For instance, the electron

configuration for copper is

[Ar] 4s1 3d5

rather than the expected

[Ar] 4s2 3d4.

Some Anomalies

This occurs because the 4s

and 3d orbitals are very
close in energy.

These anomalies occur in f-

block atoms, as well.