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
of Atoms
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 Waves

• The distance between corresponding points

on adjacent waves is the wavelength ().

Electronic
Structure
of Atoms
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 Waves
• The number of waves
passing a given point per unit
of time is the frequency ().

Electronic
Structure
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 WHAT IS ORBIT and ORBITAL? IS IT ENOUGH TO KNOW
ORBITAL CONCEPT TO UNDERSTAND ORBITALS?
An orbit is a regular, repeating path that one object in space
takes around another one.
Many planets have moons that orbit them.
http://www.nasa.gov/audience/forstudents/5-8/features/nasa-knows/what-is-
orbit-58.html

A simple view of the atom looks similar and you may have
pictured the electrons as orbiting around the nucleus. The
truth is different, and electrons in fact inhabit regions of
space known as orbitals.
Orbits and orbitals sound similar, but they have quite different
meanings. It is essential that you understand the difference
between them. http://www.chemguide.co.uk/atoms/properties/atomorbs.html

Electronic
Structure
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To plot a path for something you need to know exactly where
the object is and be able to work out exactly where it's going to
be an instant later. You can't do this for electrons.
The Heisenberg Uncertainty Principle says - loosely - that
you can't know with certainty both where an electron is and
where it's going next.
similar in structure to the solar system, but with attraction
provided by electrostatic forces rather than gravity.

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Electronic
https://en.wikipedia.org/wiki/Bohr_model Structure
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 Bohr's Model of the Atom

Niels Bohr (1913):

-studied the light produced when atoms were
excited by heat or electricity

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Structure
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 Bohr's Model of the Atom

Niels Bohr (1913):

-studied the light produced when atoms were
excited by heat or electricity

Rutherford's model couldn't explain why

unique colours were obtained by atoms of
different elements

Bohr proposed that electrons are in orbits & when

excited jump to a higher orbit. When they fall back
to the original they give off light
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Structure
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 Bohr's Model of the Atom
Bohr's model:
-electrons around the nucleus

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Structure
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 Bohr's Model of the Atom
Bohr's model:
- electrons around the nucleus
-each orbital can hold a specific maximum
number of electrons
- electrons fill orbitals closest to the nucleus
first.

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Structure
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1. Principal Quantum Number (n)

• The principal quantum number, n,

describes the energy level on which the
orbital resides.
• These correspond to the values in the
Bohr model.

Electronic
Structure
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 2. Angular Momentum Quantum
Number (l)
• This quantum number defines the shape of
the orbital.
• 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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3. Magnetic Quantum Number (ml)

• The magnetic quantum number describes the

three-dimensional orientation of the orbital.
• For 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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Electrons move in every direction, but they are limited to their own area, and this is what we
call shells.
Shells are divided into subshells. Each of these subshells (s, p, d and f) can hold a
specific maximum numbers of electrons: s =2, p = 6, d=10, and f = 14. These
subshells are further divided into orbitals. Orbitals are regions within an atom that
the electron will most likely occupy. Each subshell has a specific number of
orbitals: s = 1 orbital, p = 3 orbitals, d = 5 orbitals and f = 7 orbitals. One orbital can
contain a maximum number of two electrons.

Electronic
Structure
of Atoms
http://study.com/academy/lesson/electron-orbital-definition-shells-shapes.html
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 There are four types of subshells. Namely, s, p, d, and f.

If your shell is n = 1, then the energy level is 1 and it has 1 subshell.

If the n = 2, then it has 2 subshells.
In the figure below, if n = 1, there is only one subshell, and that is s.
When n = 2, there are 2 subshell, and these are s and p.
If n = 3, there are 3 subshells, and these are s, p, and d.
If n = 4, there are 4 subshells, and those are s, p, d, and f.
If you refer to the figure below, each box on the shell zooms in and shows how many subshells
there are.

Electronic
Structure
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 Now that we have been acquainted and re-introduced to the
terms, shells, subshells, and orbitals, we can

Electronic
Structure
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 s Orbitals

• They are spherical in shape.

• The radius of the sphere increases with the
value of n.

Electronic
Structure
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The orbital occupied by the hydrogen electron is called
a 1s orbital. The "1" represents the fact that the orbital
is in the energy level closest to the nucleus.
The "s" tells you about the shape of the orbital.

The orbital on the left is a 2s

orbital.This is similar to a 1s
orbital except that the region
where there is the greatest
chance of finding the electron is
further from the nucleus - this is
an orbital at the second energy
level.
Electronic
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 Hydrogen's electron-the 1s orbital

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 doing this 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.

95% of the time (or any other percentage you choose), the 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 region of space in which the electron lives.

Electronic
Structure
of Atoms
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 p Orbitals
• They have two lobes with a node between them.

Electronic
Structure
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 Not all electrons inhabit s
orbitals (in fact, very few
electrons live in s orbitals). At
the first energy level, the only
orbital available to electrons is
the 1s orbital, but at the second
level, as well as a 2s orbital,
there are also orbitals called 2p
orbitals.

Electronic
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 d Orbitals

• Four of the five d

orbitals have four
lobes; the other
resembles a p
orbital with a
doughnut around
the center.

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Structure
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 f Orbitals

• Very complicated shapes (not shown

in text)

Electronic
Structure
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 d and f orbitals
In addition to s and p orbitals, there are two other sets of
orbitals which become available for electrons to inhabit at
higher energy levels. At the third level, there is a set of
five d orbitals (with complicated shapes and names) as
well as the 3s and 3p orbitals

At the fourth level, as well the 4s and 4p and 4d orbitals

there are an additional seven f orbitals - 16 orbitals in
all. s, p, d and f orbitals are then available at all higher
energy levels as well.

Electronic
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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
 "Electrons-in-boxes"

A 1s orbital holding 2 electrons would be drawn as shown on the

right, but it can be written even more quickly as 1s2. This is read as
"one s two" - not as "one s squared".

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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;

Electronic
Structure
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 Electron Configurations
• The way electrons are distributed in an
4p5 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
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 Electron Configurations
• The way electrons are distributed in an
4p5 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
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 Orbital Diagrams
• Each box in the
diagram represents
one orbital.
• Half-arrows represent
the electrons.
• The direction of the
Atomic
arrow represents the number
relative spin of the
electron. Atomic
weight
Electronic
Structure
of Atoms
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 Hund’s Rule
• It only applies where the
orbitals have exactly the
same energies (as with p
orbitals, for example), and
helps to minimise the
repulsions between
electrons and so makes the
atom more stable.
http://www.chemguide.co.uk/atoms/properties/atomorbs.html

 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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 The order of filling orbitals

Notice that the s orbital always has a slightly lower energy than the p orbitals at the same energy level, so
the s orbital always fills with electrons before the corresponding p orbitals.
The real oddity is the position of the 3d orbitals. They are at a slightly higher level than the 4s - and so it is
the 4s orbital which you fill first, followed by all the 3d orbitals and then the 4p orbitals.
Similar confusion occurs at higher levels, with so much overlap between the energy levels that you don't
fill the 4f orbitals until after the 6s, for example.

Electronic
Structure
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 The order of filling orbitals

Basic
energy
level

Electronic
Structure
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B1&espv=2&biw=1366&bih=667&source=lnms&tbm=isch&sa=X&ved=0CAYQ_AUoAWoVChMIyO_LtJr of Atoms
gyAIVSZEsCh2tmAdL&dpr=1#imgrc=NPtUab-x4kY8ZM%3A
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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 (değerlik
elektronları). These are the electrons that are
transferred or shared when atoms bond together.
• 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
of Atoms
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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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