CHEMISTRY

Chapter 6
Electronic Structure of
Atoms

The Wave Nature of Light

All waves have a characteristic
wavelength, , and amplitude, A.
The frequency, v, of a wave is the
number of cycles which pass a point
in one second.

The Wave Nature of Light

The speed of a wave, v, is given by
its frequency multiplied by its
wavelength: v = v
For light, speed = c (3 x 108 m/s)

The Wave
Nature of
Light

The Wave Nature of Light

The Wave Nature of Light

Modern atomic theory arose out of
studies of the interaction of radiation
with matter.
Electromagnetic radiation moves
through a vacuum with a speed of
2.99792458 108 m/s.

The Wave Nature of Light

Electromagnetic waves have
characteristic wavelengths and
frequencies.
Example: visible radiation has
wavelengths between 400 nm (violet)
and 750 nm (red).

The Wave Nature of Light

The Wave Nature of Light

Quantized Energy and

Photons
Planck: energy can only be absorbed
or released from atoms in certain
amounts called quanta.
The relationship between energy and
frequency is E = hv

Quantized Energy and

Photons
where h is Plancks constant (6.626 10-34
J.s).
To understand quantization consider
walking up a ramp versus walking up
stairs:
For the ramp, there is a continuous change in
height whereas up stairs there is a quantized
change in height.

Quantized Energy and

Photons
The Photoelectric Effect and Photons
The photoelectric effect provides
evidence for the particle nature of
light -- quantization.
If light shines on the surface of a
metal, there is a point at which
electrons are ejected from the metal.

Quantized Energy and

Photons
The electrons will only be ejected once
the threshold frequency is reached.
Below the threshold frequency, no
electrons are ejected.
Above the threshold frequency, the
number of electrons ejected depend
on the intensity of the light.

Quantized Energy and

Photons
The Photoelectric Effect and Photons
Einstein assumed that light traveled
in energy packets called photons.
The energy of one photon: E = hv

Line Spectra and the Bohr

Model

Line Spectra
Radiation composed of only one
wavelength is called monochromatic.
Radiation that spans a whole array of
different wavelengths is called
continuous.

Line Spectra and the Bohr

Model

Line Spectra
White light can be separated into a
continuous spectrum of colors.
Note that there are no dark spots on
the continuous spectrum that would
correspond to different lines.

Line Spectra and the Bohr

Model
Bohr Model
Rutherford assumed the electrons
orbited the nucleus analogous to
planets around the sun.
However, a charged particle moving
in a circular path should lose energy.

Line Spectra and the Bohr

Model

Bohr Model
This means that the atom should be
unstable according to Rutherfords theory.
Bohr noted the line spectra of certain
elements and assumed the electrons were
confined to specific energy states. These
were called orbits.

Line Spectra and the Bohr

Model
Bohr Model
Colors from excited gases arise because
electrons move between energy states in the
atom.

Line Spectra and the Bohr

Model

Bohr Model
Since the energy states are quantized,
the light emitted from excited atoms
must be quantized and appear as line
spectra.
n is the principal quantum number
(i.e., n = 1, 2, 3, and nothing else).

Line Spectra and the Bohr

Model
Bohr Model
The first orbit in the Bohr model has n
= 1, is closest to the nucleus, and has
negative energy by convention.
The furthest orbit in the Bohr model
has n close to infinity and
corresponds to zero energy.

Line Spectra and the Bohr

Model
Bohr Model
Electrons in the Bohr model can only
move between orbits by absorbing
and emitting energy in quanta (h).
The amount of energy absorbed or
emitted on movement between states
is given by
E E E h

Line Spectra and the Bohr

Model
Limitations of the Bohr Model
Can only explain the line spectrum of
hydrogen adequately.
Electrons are not completely
described as small particles.

The Wave Behavior of

Matter
Knowing that light has a particle
nature, it seems reasonable to ask if
matter has a wave nature.
Using Einsteins and Plancks
equations, de Broglie showed:

mv

The Wave Behavior of

Matter
The momentum, (mass x velocity)mv,
is a particle property, whereas is a
wave property.
de Broglie summarized the concepts
of waves and particles, with
noticeable effects if the objects are
small.

The Wave Behavior of

Matter
The Uncertainty Principle
Heisenbergs Uncertainty Principle: It is
impossible to know exactly both the
velocity and position of a particle at
the same time.

The Wave Behavior of

Matter
The Uncertainty Principle
As the measurement of the velocity
is made more accurately, the
measurement of the position must
be less accurate.

Quantum Mechanics and

Atomic Orbitals
Schrdinger proposed an equation
that contains both wave and particle
terms.
Solving the equation leads to wave
functions.

Quantum Mechanics and

Atomic Orbitals
The wave function gives the shape of
the electronic orbital.
The square of the wave function,
gives the probability of finding the
electron,
that is, gives the electron density for
the atom.

Quantum Mechanics and

Atomic Orbitals

Quantum Mechanics
and Atomic Orbitals
Orbitals and Quantum Numbers
If we solve the Schrdinger equation,
we get wave functions and energies
for the wave functions.
We call wave functions orbitals.

Quantum Mechanics
and Atomic Orbitals
Orbitals and Quantum Numbers
Schrdingers equation requires 3
quantum numbers:
Principal Quantum Number, n. This is
the same as Bohrs n. As n becomes
larger, the atom becomes larger and the
electron is further from the nucleus.

Quantum Mechanics and

Atomic Orbitals
Orbitals and Quantum Numbers
Azimuthal Quantum Number, l. This
quantum number depends on the value
of n. The values of l begin at 0 and
increase to (n - 1). We usually use
letters for l (s, p, d and f for l = 0, 1, 2,
and 3). Usually we refer to the s, p, d
and f-orbitals.

Quantum Mechanics and

Atomic Orbitals
Orbitals and Quantum Numbers
Magnetic Quantum Number, ml. This
quantum number depends on l. The
magnetic quantum number has integral
values between -l and +l. Magnetic
quantum numbers give the 3D
orientation of each orbital.

Quantum Mechanics and

Atomic Orbitals
Orbitals and Quantum Numbers

Quantum Mechanics and

Atomic Orbitals
Orbitals can be ranked in terms of
energy to yield an Aufbau diagram.
Note that the following Aufbau diagram
is for a single electron system.
As n increases, note that the spacing
between energy levels becomes
smaller.

Quantum Mechanics and

Atomic Orbitals
Orbitals and Quantum Numbers

Quantum
Mechanics and
Atomic
Orbitals
Orbitals and Quantum Numbers

Representations of
Orbitals
The s-Orbitals
All s-orbitals are spherical.
As n increases, the s-orbitals get
larger.
As n increases, the number of nodes
increase.

Representations of
Orbitals
A node is a region in space where the
probability of finding an electron is
zero.
At a node, 2 = 0
For an s-orbital, the number of nodes
is (n - 1).

Representations of
Orbitals

Representations of
Orbitals
The s-Orbitals

Representations of
Orbitals
The p-Orbitals
There are three p-orbitals px, py, and pz.
The three p-orbitals lie along the x-, yand z- axes of a Cartesian system.
The letters correspond to allowed
values of ml of -1, 0, and +1.

Representations of
Orbitals
The p-Orbitals
The orbitals are dumbbell shaped.
As n increases, the p-orbitals get
larger.
All p-orbitals have a node at the
nucleus.

Representations of
Orbitals
The p-Orbitals

Representations of
Orbitals
The d and f-Orbitals
There are five d and seven f-orbitals.
Three of the d-orbitals lie in a plane
bisecting the x-, y- and z-axes.
Two of the d-orbitals lie in a plane
aligned along the x-, y- and z-axes.

Many-Electron Atoms

Orbitals and Their Energies

Orbitals of the same energy are said to be
degenerate.
For n 2, the s- and p-orbitals are no longer
degenerate because the electrons interact
with each other.
Therefore, the Aufbau diagram looks slightly
different for many-electron systems.

Orbitals and Their Energies

Many-Electron Atoms

Many-Electron Atoms
Electron Spin and the Pauli Exclusion
Principle
Line spectra of many electron atoms
show each line as a closely spaced
pair of lines.
Stern and Gerlach designed an
experiment to determine why.

Many-Electron Atoms
A beam of atoms was passed through
a slit and into a magnetic field and
the atoms were then detected.
Two spots were found: one with the
electrons spinning in one direction
and one with the electrons spinning
in the opposite direction.

Many-Electron Atoms
Electron Spin and the Pauli Exclusion
Principle

Many-Electron Atoms
Electron Spin and the Pauli Exclusion Principle

Since electron spin is quantized, we define ms

= spin quantum number = .
Paulis Exclusions Principle: no two electrons
can have the same set of 4 quantum numbers.

Therefore, two electrons in the same orbital must hav

opposite spins.

Electron Configurations
Hunds Rule
Electron configurations tells us in
which orbitals the electrons for an
element are located.

Electron Configurations
Three rules:
electrons fill orbitals starting with lowest n
and moving upwards;
no two electrons can fill one orbital with
the same spin (Pauli);
for degenerate orbitals, electrons fill each
orbital singly before any orbital gets a
second electron (Hunds rule).

Electron Configurations
Condensed Electron Configurations
Neon completes the 2p subshell.
Sodium marks the beginning of a new
row.
So, we write the condensed electron
configuration for sodium as
Na: [Ne] 3s1

Electron Configurations
Condensed Electron Configurations
[Ne] represents the electron
configuration of neon.
Core electrons: electrons in [Noble
Gas].
Valence electrons: electrons outside of
[Noble Gas].

Electron Configurations

Transition Metals
After Ar the d orbitals begin to fill.
After the 3d orbitals are full, the 4p
orbitals being to fill.
Transition metals: elements in which the
d electrons are the valence electrons.

Electron Configurations
Lanthanides and Actinides
From Ce onwards the 4f orbitals begin
to fill.
Note: La: [Xe]6s25d14f0
Elements Ce - Lu have the 4f orbitals
filled and are called lanthanides or rare
earth elements.

Electron Configurations
Lanthanides and Actinides
Elements Th - Lr have the 5f orbitals
filled and are called actinides.
Most actinides are not found in
nature.

Electron Configurations
and the Periodic Table
The periodic table can be used as a
guide for electron configurations.
The period number is the value of n.
Groups 1A and 2A have the s-orbital
filled.

Electron Configurations
and the Periodic Table
Groups 3A - 8A have the p-orbital
filled.
Groups 3B - 2B have the d-orbital
filled.
The lanthanides and actinides have
the f-orbital filled.

End of Chapter 6:
Electronic Structure of
Atoms