Quantum chemistry:

Electronic Structure
of Atoms
 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 ().
• The square of the wave
equation, 2, 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.
 Quantum Numbers
Each electron in an atom has a unique set of 4
quantum numbers which describe it.

 Principal quantum number

 Angular momentum quantum number
 Magnetic quantum number
 Spin quantum number
 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.
 Electron Energy Level (Shell)
Generally symbolized by
n, it denotes the probable
distance of the electron
from the nucleus. “n” is
also known as the
Principle Quantum
number

Number of electrons that

can fit in a shell:
2n2
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.
Angular Momentum Quantum Number
(l)
Value of l 0 1 2 3
Type of orbital s p d f

Electron Orbitals

An orbital is a region within an energy level where there is a probability of finding

an electron.

Orbital shapes are defined as the surface that contains 90% of the total
electron probability.

The angular momentum quantum number, generally symbolized by l, denotes the

orbital (subshell) in which the electron is located.
 s Orbital shape

The s orbital
(l = 0) has a spherical
shape centered
around
the origin of the three
axes in space.
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.
 s Orbitals Movie
Radial Electron Distribution
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.

© 2009, Prentice-Hall, Inc.

 p orbital shape

There are three dumbbell-shaped (two lobes with a

node between them) p orbitals (l = 1) in each
energy level above n = 1, each assigned to its own
axis (x, y and z) in space.
d orbital shapes
Things get a bit more
complicated with the five d
orbitals (l = 2) that are found
in the d sublevels beginning
with n = 3. To remember the
shapes, think of “double
dumbells”

…and a “dumbell
with a donut”!
Shape of f (l = 3) orbitals
 Magnetic Quantum Number
The magnetic quantum number, generally symbolized
by m, denotes the orientation of the electron’s orbital
with respect to the three axes in space.
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, etc.
Magnetic Quantum Number (ml)

• Orbitals with the same value of n form a shell.

• Different orbital types within a shell are subshells.
Orbital filling table
 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.

© 2009, Prentice-Hall, Inc.

 Pauli Exclusion Principle

Two electrons occupying

the same orbital must
have opposite spins

Wolfgang
Pauli
 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.

© 2009, Prentice-Hall, Inc.

 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.

© 2009, Prentice-Hall, Inc.

 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.

© 2009, Prentice-Hall, Inc.

 Electron Spin
The Spin Quantum Number describes
the behavior (direction of spin) of an
electron within a magnetic field.

Possibilities for electron spin:

1 1
 
2 2
 Assigning the Numbers
 The three quantum numbers (n, l, and m) are
integers.
 The principal quantum number (n) cannot be
zero.
 n must be 1, 2, 3, etc.
 The angular momentum quantum number (l )
can be any integer between 0 and n - 1.
 For n = 3, l can be either 0, 1, or 2.
 The magnetic quantum number (ml) can be any
integer between -l and +l.
 For l = 2, m can be either -2, -1, 0, +1, +2.
Electron Configurations
• This shows the
distribution of all
electrons in an atom.
• Each component consists
of
– A number denoting the
energy level,

© 2009, Prentice-Hall, Inc.

Electron Configurations
• This shows the
distribution of all
electrons in an atom
• Each component consists
of
– A number denoting the
energy level,
– A letter denoting the type
of orbital,

© 2009, Prentice-Hall, Inc.

Electron Configurations
• This shows the
distribution of all
electrons in an atom.
• 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.

© 2009, Prentice-Hall, Inc.

 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.

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Hund’s Rule

“For degenerate
orbitals, the lowest
energy is attained
when the number of
electrons with the
same spin is
maximized.”

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 Periodic Table

• We fill orbitals in
increasing order of
energy.
• Different blocks on the
periodic table (shaded in
different colors in this
chart) correspond to
different types of
orbitals.

© 2009, Prentice-Hall, Inc.

 Element Configuration Orbital notation Noble gas
notation notation
Lithium 1s22s1 [He]2s1
____ ____ ____ ____ ____
1s 2s 2p
Beryllium 1s22s2 [He]2s2
____ ____ ____ ____ ____
1s 2s 2p
Boron 1s22s22p1 [He]2s2p1
____ ____ ____ ____ ____
1s 2s 2p
Carbon 1s22s22p2 [He]2s2p2
____ ____ ____ ____ ____
1s 2s 2p
Nitrogen 1s22s22p3 [He]2s2p3
____ ____ ____ ____ ____

1s 2s 2p
Oxygen 1s22s22p4 [He]2s2p4
____ ____ ____ ____ ____
1s 2s 2p
Fluorine 1s22s22p5 [He]2s2p5
____ ____ ____ ____ ____
1s 2s 2p
Neon 1s22s22p6 [He]2s2p6
____ ____ ____ ____ ____
1s 2s 2p
Some Anomalies

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

© 2009, Prentice-Hall, Inc.

Some Anomalies

For instance, the

electron
configuration for
copper is
[Ar] 4s1 3d10
rather than the
expected
[Ar] 4s2 3d9.

© 2009, Prentice-Hall, Inc.

Some Anomalies

• This occurs
because the 4s and
3d orbitals are very
close in energy.
• These anomalies
occur in f-block
atoms, as well.

© 2009, Prentice-Hall, Inc.

 Let’s try:

Oxygen Lanthanum

Potassium Thallium

Copper Bromine

Rhenium Iodine