Unit IV: Quantum

Mechanics and Bonding

 Light
• Before 1900, scientists thought that
light behaved only as wave
• discovered that also has particle-like
characteristics
 Light as a Wave
• electromagnetic radiation:
– form of energy that acts as a wave as it
travels
– includes: visible light, X rays, ultraviolet
and infrared light, microwaves, and radio
waves
• All forms are combined to form
electromagnetic spectrum
Light as a Wave
 Light as a Wave
• all form of EM radiation travel at a
speed of 3.0 x 108 m/s in a vacuum
• it has a repetitive motion
• wavelength: (λ) distance between
points on adjacent waves; in nm
(109nm = 1m)
• frequency: (ν) number of waves that
passes a point in a second, in
waves/second

Inversely proportional!
c = λυ
 Photoelectric Effect
• when light is shone on a piece of
metal, electrons can be emitted
• no electrons were emitted if the
light’s frequency was below a certain
value
• scientists could not explain this with
their classical theories of light
• Ex: coin-operated sift drink machine
 Photoelectric Effect
• Max Planck: a German physicist
• suggested that an object emits
energy in the form of small packets of
energy called quanta
• quantum- the minimum amount of
energy that can be gained or lost by
an atom
E = hν
Planck’s constant (h): 6.626 x 10-34 J*s
 Photoelectric Effect
• Einstein added on to Planck’s theory
in 1905
• suggested that light can be viewed
as stream of particles
• photon- particle of EM radiation
having no mass and carrying one
quantum of energy
• energy of photon depends on
frequency
 Photoelectric Effect
• EM radiation can only be absorbed by
matter in whole numbers of photons
• when metal is hit by light, an
electron must absorb a certain
minimum amount of energy to knock
the electron loose
• this minimum energy is created by a
minimum frequency
• since electrons in different metal
atoms are bound more or less tightly,
then they require more or less
 H Line-Emission Spectrum
• ground state- lowest energy state of
an atom
• excited state- when an atom has
higher potential energy than it has at
ground state
• line-emission spectrum- series of
wavelengths of light created when
visible portion of light from excited
atoms is shined through a prism
 H Line-Emission Spectrum
• scientists using classical theory
expected atoms to be excited by
whatever energy they absorbed
• continuous spectrum- emission of
continuous range of frequencies of EM
radiation
 H Line-Emission Spectrum
• Why had hydrogen atoms only given
off specific frequencies of light?
current Quantum Theory attempts to
explain this using a new theory of atom
 H Line-Emission Spectrum
• when an excited atom falls back to
ground state, it emits photon of
radiation
• the photon is equal to the difference
in energy of the original and final
states of atom
• since only certain frequencies are
emitted, the differences between the
states must be constant
 Bohr Model
• created by Niels Bohr
(Danish physicist)
in 1913
• linked atom’s electron with emission
spectrum
• electron can circle nucleus in certain
paths, in which it has a certain
amount of energy
 Bohr Model
• Can gain energy by
moving to a higher
rung on ladder
• Can lose energy by
moving to lower rung
on ladder
• Cannot gain or lose
while on same rung of
ladder
 Bohr Model
a photon is
released that
has an energy
equal to the
difference
between the
initial and final
energy orbits
 Bohr Model
• problems:
– did not work for other atoms
– did not explain chemical behavior
of atoms
Introduction to Quantum Theor

• Quantum Theory-
describes mathematically the wave
properties of electrons
 Electrons as Waves
• In 1924, Louis de Broglie
(French scientist)
• suggested the way quantized
electrons orbit the nucleus is similar to
behavior of wave
• electrons can be seen as waves
confined to the space around a nucleus
• waves could only be certain
frequencies since electrons can only
have certain amounts of energy
 Electrons as Waves
c
c = λv v=
λ hc
E=
λ
E = hv
h hc
λ= = mc 2

mv λ E = mc 2

shows that anything with both mass and

velocity has a corresponding wavelength
Uncertainty Principle
• In 1927 by Werner Heisenberg
(German theoretical physicist)
• electrons can only be detected by
their interaction with photons
• any attempt to locate a specific
electron with a photon knocks the
electron off course
• Heisenberg Uncertainty Principle- it is
impossible to know both the position
and velocity of an electron
 Schrödinger Wave
Equation
• In 1926, Erwin Schrödinger
(Austrian physicist)
• his equation proved that
electron energies are quantized
• only waves of specific energies
provided solutions to his equation
• solutions to his equation are called
wave functions
 Schrödinger Wave
Equation
• wave functions give only the
probability of finding an electron in a
certain location

• orbital- 3D area around a nucleus

that has a high probability of
containing an electron
• orbitals have different shapes and
sizes
 Quantum Numbers
• specify the properties of atomic
orbitals and of electrons in orbitals
• the first three numbers come from
the Schrödinger equation and
describe:
– main energy level
– shape
– orientation
• 4th describes state of electron
 1 Quantum Number
st

Principal Quantum Number: n

• main energy level occupied by
electron
• values are all positive integers
(1,2,3,…)
• As n increases, the electron’s energy
and its average distance from the
nucleus increase
• multiple electrons are in each level
so have the same n value
• the total number of orbitals in a level
 1 Quantum Number
st

Energy
 2 nd
Quantum Number
Angular Momentum Quantum
Number: l
• indicates the shape of the orbital
(sublevel)
• the possible values of l are 0 to n-1
• each atomic orbital is designated by the
principal quantum number followed by
the letter of the sublevel
 2 nd
Quantum Number

s orbitals:
• spherical
• l value of 0
• Max 2 electronsd
 2 nd
Quantum Number

p orbitals:
• dumbbell-shaped
• l value of 1
• Max. 6 electrons
 2 nd
Quantum Number

d orbitals:
• various shapes
• l value of 2
• Max. 10 electrons
 2 nd
Quantum Number

f orbitals:
• various shapes
• l value of 3
• Max. 14 electrons
 2 nd
Quantum Number

L Sublevel Subleve
evel s ls

0 1 2
3

0 1 2

0 1

0
 3 Quantum Number
rd

Magnetic Quantum Number: ml

• indicates the orientation of an orbital
around the nucleus
• has values from -l +l
• specifies the exact orbital that the
electron is contained in
• each orbital holds maximum of 2
electrons
Energy Sublevel # Total #
Level s in Level Orbitals of
(n) in Orbitals
Sublevel in Level
1 l=0, s 1 1
2 l=0, s 1 4
l=1, p 3
3 l=0, s 1 9
l=1, p 3
l=2, d 5
4 l=0, s 1 16
l=1, p 3
l=2, d 5
l=3, f 7
 4 Quantum Number
th

Spin Quantum Number: ms

• indicates the spin state of the
electron
• only 2 possible directions
• only 2 possible values: -½ and +½
• paired electrons must
have opposite spins
 Energy Level 1
n l ml ms
1 0 0 -½,+½
 Energy Level 2
n l ml ms

2 0 0 -½,+½

1 -1 -½,+½

0 -½,+½

+1 -½,+½
 Energy Level 3
n l ml ms
3 0 0 -½,+½
1 -1 -½,+½
0 -½,+½
+1 -½,+½
2 -2 -½,+½
-1 -½,+½
0 -½,+½
+1 -½,+½
+2 -½,+½
 Energy Level 4
n l ml ms l ml ms
4 0 0 -½,+½ 3 -3 -½,+½
1 -1 -½,+½
-2 -½,+½
0 -½,+½
+1 -½,+½ -1 -½,+½
2 -2 -½,+½ 0 -½,+½
-1 -½,+½ +1 -½,+½
0 -½,+½
+2 -½,+½
+1 -½,+½
+2 -½,+½ +3 -½,+½
 Homework
1. Give the values of n, ℓ, mℓ and ms for
every orbital with n = 6.
2. Indicate whether the set of quantum
numbers (n, ℓ, mℓ) exits or not.
a. 1, 1, 0 e. 8, 1, 0
b. 5, 4, –3 f. –2, 1, +1
c. 3, 2, –3 g. 4, 2, –1
d. 6, 7, +7 h. 7, 3, +4
3. Draw the shapes (including the
orientation) of all the s, p and d orbitals.
 Homework
4. Which orbital in each of the following pairs is
higher in energy?
a. 5s or 5d
b. 4s or 3p
c. 6s or 4d
5. What is the maximum number of electrons in an
atom that can have these quantum numbers?
a) n = 2
b) n = 3,
c) n = 3, l = 1
d) n = 4, l = 2
e) n = 5, l= 3, ml=3