Lecture Presentation

Chapter 6

Electronic
Structure of Atoms

James F. Kirby Electronic

Quinnipiac University Structure
of Atoms
© 2015 Pearson Education Hamden, CT
 Electronic Structure
• This chapter is all about electronic
structure—the arrangement and
energy of electrons.
• It may seem odd to start by talking
about waves. However, extremely small
particles have properties that can only
be explained in this manner!

Electronic
Structure
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 Waves
Waves are a periodic variation of some quantity.

For example for water waves below, the periodic variation is water level.

Electronic
Structure
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 The Wave Nature of Light
Many of the features of light that we encounter can be explained as properties of waves.
The periodic variation in the case of light is electric field.

• Wavelength, , is the distance between two corresponding points on a wave.

• Amplitude is the size or “height” of a wave.

• Frequency, , is the number of cycles of the wave passing a given point per second,Electronic
Structure
usually expressed in Hz.
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 The Wave Nature of Light
Visible Light is a small portion of electromagnetic radiation, which consists of
oscillating electric and magnetic fields.

Electromagnetic radiation includes radio waves, microwaves and X-rays.

Electronic
Structure
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 The Wave Nature of Light

The fourth variable of light is velocity.

All light has the same speed in a vacuum.

c = 2.99792458 x 108 m/s

The product of the frequency and wavelength is the speed of light.

Frequency is inversely proportional to wavelength.

Electronic
Structure
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 The Wave Nature of Light
Refraction is the bending of light when it passes from one medium to another of different density.

• Speed of light changes.

• Light bends at an angle depending on its wavelength.

• Light separates into its component colors.

Electronic
Structure
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 The Nature of Energy

Electronic
Structure
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 The Black Body Radiation and the UV Catastrophe
What is a black body?

A black body is an idealized physical body that absorbs all incident electromagnetic
radiation, regardless of frequency or angle of incidence.

Black body radiation : Black-body radiation is

the type of electromagnetic radiation within
or surrounding a body in thermodynamic
equilibrium with its environment, or emitted
by a black body held at constant, uniform
temperature.

Electronic
Structure
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The Black Body Radiation and the UV Catastrophe

Electronic
Structure
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 The Photoelectric Effect

• Einstein used this the idea of quantized energy(in his case light energy) to explain
photoelectric effect.
Electronic
Structure
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 The Photoelectric Effect

When light shined on a metal surface,

electrons are ejected.

The amount of electrons can be

determined by measuring the current
with an apparatus shown on the left.

However some phenomenon observed

in this experiment was inconsistent
with the well established Maxwell's
theory of electromagnetism (The wave
nature of light).

Electronic
Structure
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 The Photoelectric Effect: The Particle Nature of Light
If light is made up waves then it should be expected that the energy content of light is
continuous. This would imply that;

• It would be a matter of time before an electron would acquire enough energy to

become free from nuclear attraction. This does not occur. In fact unless emission
occurs instantaneously and simultaneously with the irradiation of light it would
not occur at all.

• Emission would occur at any frequency. In fact it does not. Emission is frequency
related.

• Increasing the frequency will increase number of electrons emitted. This is not
the case.

• It would be expected that in the consequence that the intensity of the light is
low no emission would occur. Still from observations it is seen that using the
right frequency of light, emission would still be obtained. Electronic
Structure
of Atoms
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 The Photoelectric Effect: The Particle Nature of Light

All these observations were explained by Einstein’s theory of photons!

Einstein proposed light to be made up of quantized packets of energy (Planck’s

Theory) which he referred to as photons. Accordingly these photons had an energetic
content related to the frequency. That is the higher the frequency the higher would
be the energetic content.

• Einstein proposed that an electron would be emitted only if it is hit by a photon

and the energy of the photon is absorbed. In the consequence of a collision the
electron would absorb all of the energy of the photon or none at all.

• Energy cannot be shared between electrons.

• Consequently the amount of emitted electrons is proportional to the intensity or Electronic

Structure
number of incident photons. of Atoms
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 The Particulate Nature of Light

• The energy of a photon (E) is proportional to the frequency ().

• and is inversely proportional to the wavelength ( ).

• h = Planck’s constant = 6.626 x 10 -34 J s

Electronic
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 The Particulate Nature of Light

Binding Energy - energy holding an electron to a metal.

Threshold frequency, νo - minimum frequency of light needed to emit an electron.

For frequencies below the threshold frequency, no electrons are emitted.

For frequencies above the threshold frequency, extra energy is imparted to the electrons as
kinetic energy.

Ephoton = Binding E + Kinetic E

Electronic
Structure
of Atoms
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 The Photoelectric Effect

a) For  > 0, the number of electrons emitted is

independent of frequency.
Value of 0 depends on metal used.

b) As light intensity increases, the number of

photoelectrons increases.

c) As frequency increases, kinetic energy of emitted

electrons increases linearly.

d) The kinetic energy of emitted electrons is

independent of light intensity.

Electronic
Structure
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 The Particulate Nature of Light

• The photoelectric effect is not explained using a wave description but is

explained by modeling light as a particle.

• Particles of light are called photons.

• Wave-particle duality - depending on the situation, light is best described as

a wave or a particle.

• Light is best described as a particle when light is imparting energy to another

object.

• Neither waves nor particles provide an accurate description of all the

properties of light. Use the model that best describes the properties being
examined.

Electronic
Structure
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 Atomic Emissions
Another mystery in the early twentieth century
involved the emission spectra observed from
energy emitted by atoms and molecules.

Electronic
Structure
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 Continuous vs. Line Spectra
• For atoms and molecules,
one does not observe a
continuous spectrum
(the “rainbow”), as one
gets from a white light
source.
• Only a line spectrum of
discrete wavelengths is
observed. Each element
has a unique line
spectrum.
Electronic
Structure
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 The Hydrogen Spectrum

• Johann Balmer (1885) discovered a

simple formula relating the four lines to
integers.
• Johannes Rydberg advanced this
formula.

• Neils Bohr explained why this

mathematical relationship works. Electronic
Structure
of Atoms
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 The Bohr Model
• 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).

Electronic
Structure
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 The Bohr Model
2. Electrons in permitted orbits
have specific, “allowed”
energies; these energies will not
be radiated from the atom.
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 = h

Electronic
Structure
of Atoms
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 The Bohr Model
The energy absorbed or emitted
from the process of electron
promotion or demotion can be
calculated by the equation
1 1
E = −hcRH ( nf2
–
ni2 )
where RH is the Rydberg
constant, 1.097  107 m−1, and ni
and nf are the initial and final
energy levels of the electron.Electronic
Structure
of Atoms
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 Limitations of the Bohr Model

• It only works for hydrogen!

• Classical physics would result in an
electron falling into the positively
charged nucleus. Bohr simply assumed
it would not!
• Circular motion is not wave-like in
nature.
Electronic
Structure
of Atoms
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 Important Ideas from the
Bohr Model
 Points that are incorporated into the
current atomic model include the
following:
1) Electrons exist only in certain discrete
energy levels.
2) Energy is involved in the transition of
an electron from one level to another.
Electronic
Structure
of Atoms
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 The Wave Nature of Matter
• Louis de Broglie theorized
that if light can have material
properties, matter should
exhibit wave properties.
• He demonstrated that the
relationship between mass
and wavelength was
h
The wave nature of light  = mv
is used to produce this
electron micrograph. Electronic
Structure
of Atoms
© 2015 Pearson Education
 h
 = mv

h = 6.626 10-34 J s (kg m2 s-2)

A football is 445 grams.

Fastest shot ever made: Ronny Heberson -Sporting Lisbon – 2006, 211 kmh, 58 m/s.

mass of electron: 9.10938291 × 10-31 kilograms

speed varies lets say 1 x 105 m/s (a regular speed for an electron). Electronic
Structure
Let’s calculate the wavelength for both systems. of Atoms
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 The Uncertainty Principle
Heisenberg showed
that the more precisely
the momentum of a
particle is known, the
less precisely is its
position is known:

h
(x) (mv) 
4
Electronic
Structure
of Atoms
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 The Uncertainty Principle

Electronic
Structure
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 Quantum Mechanics
• Erwin Schrödinger
developed a mathematical
treatment into which both
the wave and particle
nature of matter could be
incorporated.
• This is known as
quantum mechanics.

Electronic
Structure
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 Quantum Mechanics
• The solution of Schrödinger’s
wave equation is designated with
a lowercase Greek psi ().
• The square of the wave equation,
2, gives the electron density, or
probability of where an electron is
likely to be at any given time.

Electronic
Structure
of Atoms
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 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.
Electronic
Structure
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 Principal Quantum Number (n)

• The principal quantum number, n,

describes the energy level on which the
orbital resides.
• The values of n are integers ≥ 1.
• These correspond to the values in the
Bohr model.

Electronic
Structure
of Atoms
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 Angular Momentum 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.
Electronic
Structure
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 Angular Momentum Quantum
Number (l)

Electronic
Structure
of Atoms
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 Magnetic Quantum Number (ml)

• The magnetic quantum number describes the

three-dimensional orientation of the orbital.
• Allowed values of ml 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, and so forth.
Electronic
Structure
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 Magnetic Quantum Number (ml)
• Orbitals with the same value of n form an electron
shell.
• Different orbital types within a shell are subshells.

Electronic
Structure
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 s Orbitals

• The value of l for s orbitals is 0.

• They are spherical in shape.
• The radius of the sphere increases with the
value of n.
Electronic
Structure
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 s Orbitals
• For an ns orbital, the
number of peaks is n.
• For an ns orbital, the
number of nodes (where
there is zero probability
of finding an electron) is
n – 1.
• As n increases, the
electron density is more
spread out and there is
a greater probability of
finding an electron
further from the nucleus.
Electronic
Structure
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 p Orbitals
• The value of l for p orbitals is 1.
• They have two lobes with a node between them.

Electronic
Structure
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 d Orbitals
• The value of l for a
d orbital is 2.
• Four of the five d
orbitals have four
lobes; the other
resembles a p
orbital with a
doughnut around
the center.
Electronic
Structure
of Atoms
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 f Orbitals

• Very complicated shapes (not shown

in text)
• Seven equivalent orbitals in a sublevel
• l=3

Electronic
Structure
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 Energies of Orbitals—Hydrogen

• For a one-electron
hydrogen atom,
orbitals on the same
energy level have
the same energy.
• Chemists call them
degenerate orbitals.

Electronic
Structure
of Atoms
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 Energies of Orbitals—
Many-electron Atoms
• As the number of electrons
increases, so does the
repulsion between them.
• Therefore, in atoms with
more than one electron, not
all orbitals on the same
energy level are degenerate.
• Orbital sets in the same
sublevel are still degenerate.
• Energy levels start to overlap
in energy (e.g., 4s is lower
in energy than 3d.) Electronic
Structure
of Atoms
© 2015 Pearson Education
 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.
• This led to the spin quantum
number, ms.
• The spin quantum number has only
two allowed values, +½ and –½.
Electronic
Structure
of Atoms
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 Pauli Exclusion Principle
• No two electrons in the same atom can
have exactly the same energy.
• Therefore, no two electrons in the same
atom can have identical sets of quantum
numbers.
• This means that every electron in an atom
must differ by at least one of the four
quantum number values: n, l, ml, and ms.

Electronic
Structure
of Atoms
© 2015 Pearson Education
 Electron Configurations
• The way electrons are distributed in an
4p 5 atom is called its electron configuration.
• The most stable organization is the lowest
possible energy, called the ground state.
• Each component consists of
– a number denoting the energy level;

Electronic
Structure
of Atoms
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 Electron Configurations
• The way electrons are distributed in an
4p 5 atom is called its electron configuration.
• The most stable organization is the lowest
possible energy, called the ground state.
• Each component consists of
– a number denoting the energy level;
– a letter denoting the type of orbital;

Electronic
Structure
of Atoms
© 2015 Pearson Education
 Electron Configurations
• The way electrons are distributed in an
4p 5 atom is called its electron configuration.
• The most stable organization is the lowest
possible energy, called the ground state.
• Each component consists of
– a number denoting the energy level;
– a letter denoting the type of orbital;
– a superscript denoting the number of
electrons in those orbitals.
Electronic
Structure
of Atoms
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 Orbital Diagrams
• Each box in the
diagram represents
one orbital.
• Half-arrows represent
the electrons.
• The direction of the
arrow represents the
relative spin of the
electron.

Electronic
Structure
of Atoms
© 2015 Pearson Education
 Hund’s Rule
“For degenerate
orbitals, the
lowest energy is
attained when
the number of
electrons with
the same spin is
maximized.”

 This means that, for a set of orbitals in the same

sublevel, there must be one electron in each orbital
before pairing and the electrons have the same spin,
Electronic
as much as possible. Structure
of Atoms
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Condensed Electron Configurations
• Elements in the same group of the
periodic table have the same number
of electrons in the outer most shell.
These are the valence electrons.
• The filled inner shell electrons are
called core electrons. These include
completely filled d or f sublevels.
• We write a shortened version of an
electron configuration using brackets
around a noble gas symbol and listing
only valence electrons.
Electronic
Structure
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 Periodic Table
• We fill orbitals in increasing order of energy.
• Different blocks on the periodic table correspond to
different types of orbitals: s = blue, p = pink (s and p
are representative elements); d = orange (transition
elements); f = tan (lanthanides and actinides, or
inner transition elements)

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

Electronic
Structure
of Atoms
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 Chromium as an Anomaly
• For instance, the electron configuration
for chromium is
[Ar] 4s1 3d5
rather than the expected
[Ar] 4s2 3d4.
• This occurs because the 4s and 3d
orbitals are very close in energy.
• These anomalies occur in f-block atoms
with f and d orbitals, as well. Electronic
Structure
of Atoms
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