Chapter 2:
The Quantum-Mechanical
Model of the Atom
Wave nature of light
Wave properties
All waves are characterized by the
following:
1) Wavelength (λ)
• Distance between two consecutive
peaks or troughs in a wave.
2) Frequency ()
𝑐
• Number of successive wavelengths
𝜈=
that pass a given point in a unit
time.
𝜆
Where C is the speed of light:
3) Amplitude 3.00 x 108 m/s
• Vertical height of a crest (or depth
of a trough).
Waveleng
th
and
Amplitude
• One-dimensional sinusoidal waves show the relationship
among wavelength, frequency, and speed. The wave with the
shortest wavelength has the highest frequency. Amplitude is
one-half the height of the wave from peak to trough.
The Electromagnetic Plank’s Equation: E=
Spectrum
Common Uses of the EMS:
Please
Note:
This
scale is
the
reverse
of the
one on
the
previous
slide
High Low
Energy Energy
Interference and Diffraction
Interference and Diffraction
Interference and Diffraction
The Photoelectric Effect
An
Emission Spectra
Line spectra – Elements give off energy in the form of
light
• Each emission line consists of a
single wavelength of light.
• This implies that the light emitted by
a gas consists of a set of discrete
energies.
• The origin of discrete spectra in
atoms and molecules was extremely
puzzling to scientists.
It’s why neon signs have color
And….
Flame tests and
Fireworks!
The emitted wavelengths correspond to difference in the energy levels of
an atom
How chemists usually show electron transitions:
Excited State
Ground State
• The horizontal lines show the relative energy of orbits in the Bohr
model of the hydrogen atom, and the vertical arrows depict the
energy of photons absorbed (left) or emitted (right) as electrons
Niels Bohn Model of the Atom
1913 Niels Bohr Proposed new model of the atom with electrons in orbitals
Bohr used the atomic spectra of
hydrogen to produce his model
Rydberg constant
Hydrogen Transitions
Bohr Model of the Atom
Bohr proposed circular orbits….
Works great with Hydrogen
but when you add more electrons….
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When you add more electrons, the model fails:
Electrons repel each other!
and
The wave nature of electrons needed to be considered:
de Broglie equation: Heisenberg’s Uncertainty Prinicple:
Brief history of the uncertainty principle can be found here:
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This realization eventually leads to
our modern understanding of
orbitals and
the Schrödinger Equation:
Hamiltoniam operator
wave function
energy of the electron
The Wave Nature of Matter
(a)The interference pattern for
electrons passing through very
closely spaced slits demonstrates
that quantum particles such as
electrons can exhibit wavelike
behavior.
(b)If the electrons behaved like
particles, we would expect to see
two bright stripes with darkness in
between
Figure 2.16
The Wave Nature of Matter
The de Borglie relation: the velocity of a moving
electron
is related to its wavelength – knowing one is
equivalent to knowing the other
Wave-particle duality
While electrons are small localized particles, their
motion does not follow the equations of motion
implied by classical mechanics.
Instead, some type of wave equation governs a
probability distribution for an electron’s motion.
Thus, the wave–particle duality first observed
with photons is actually a fundamental behavior
intrinsic to all quantum particles.
Heisenberg Uncertainty Principle
Werner Heisenberg determined that there is
a fundamental limit to how accurately one can
measure both a particle’s position and its
momentum simultaneously.
The more accurately we measure the
momentum of a particle, the less accurately
we can determine its position at that time, and
vice versa.
Heisenberg Uncertainty Principle: It is
fundamentally impossible to determine
simultaneously and exactly both the
momentum and the position of a particle.
Your book has a great analogy:
The Quantum-Mechanical Model of an Atom
• Erwin Schrödinger extended de
Broglie’s work by incorporating the de
Broglie relation into a wave equation.
• Today this equation is known as the
Schrödinger equation.
• Schrödinger properly thought of the
electron in terms of a three-
dimensional stationary wave, or
wavefunction, represented by the
Greek letter psi, ψ.
The Schrodinger equation
• In the most general form, the
Schrödinger equation can be written
as:
• Ĥ is the Hamiltonian operator, a set of
mathematical operations representing the
total energy of the quantum particle.
• ψ is the wavefunction of the particle.
Quantum Mechanics (CHEM 261, CHEM 461)
• Schrödinger’s work, as well as that of
Heisenberg and many other scientists
following in their footsteps, is
generally referred to as quantum
mechanics.
Understanding Quantum Theory of Electrons
in Atoms
• Electrons in atoms can exist only in
discrete energy levels but not between
them.
• The energy of an electron in an atom is
quantized.
• The energy can be equal only to certain
specific values and can jump from one
energy level to another but not transition
smoothly or stay between these levels.
Quantum Numbers
• n = Principle Quantum Number
• Electron shell, Size of the orbital
• = Orbital Angular Momentum Quantum Number
• Shape of the subshell
• m = Magnetic Quantum Number
• 3-D Orientation in Space
• m = Electron Spin Quantum Number
• Spin of the electron “up” or “down”
Quantum Numbers
Principle quantum number,
n
• The energy levels are labeled with an
n value, where n = 1, 2, 3, ….
• The energy of an electron in an atom
is greater for larger values of n.
• n is referred to as the principal
quantum number or shell number.
• The principal quantum number defines
the location of the energy level and
is similar in concept to the Bohr model.
n is essentially how far the orbital is in space from the nucleus:
• Different shells are numbered by principal
quantum numbers. Correspond to rows of the
Atomic orbitals
• The principal quantum number is one of
three quantum numbers used to
characterize an orbital.
• An atomic orbital is a general region in
space around the nucleus that an electron
is most probable to reside.
• An atomic orbital is distinct from an orbit.
• The quantum mechanical model specifies
the probability of finding an electron in a
three-dimensional space around the
Angular Momentum Quantum Number, ℓ
• The angular momentum quantum
number (ℓ) is an integer that defines the
shape of the orbital.
• ℓ takes on the values, ℓ = 0, 1, 2, …, n –
1.
• For an orbital with n = 1; ℓ = 0
• For an orbital with n = 2; ℓ = 0 and 1
• Orbitals with the same value of ℓ form a
Angular Momentum Quantum Number, ℓ
Instead of using numbers, the angular
momentum quantum number is often
designated by letters.
• For ℓ = 0: s orbital
• For ℓ = 1: p orbitalThese are how we usually refer
to orbitals unless the class is
• For ℓ= 2: d orbital Physical Chemistry
• For ℓ = 3: f orbital
Summary of the Quantum Numbers:
Radial nodes
• There are certain distances from the
nucleus at which the probability
density of finding an electron located
in a particular orbital is zero.
• The value of the wavefunction ψ is
zero at this distance for this orbital.
• Such a value of radius r is called a
radial node.
Radial nodes
• The number of radial nodes in an orbital is n –
ℓ – 1.
• For a 1s orbital (n = 1, ℓ = 0)
• The number of nodes = 1 – 0 – 1 = 0
• For a 2s orbital (n = 2, ℓ = 0)
• The number of nodes = 2 – 0 – 1 = 1
• For a 3s orbital (n = 3, ℓ = 0)
• The number of nodes = 3 – 0 – 1 = 2
Nodes in the 2s and
3s orbitals
• These graphs show the
probability (y axis) of
finding an electron for the
2s and 3s orbitals as a
function of distance from
the nucleus.
Orbital shapes
• The s subshell has a spherical
shape.
• The p subshell has a dumbbell
shape.
• The d and f orbitals are more
complex.
• These shapes represent the three-
dimensional regions where the
electron is most likely to be found.
s
Diagram of atomic orbital
shapes
p
• Shapes of s, p, d, and f
orbitals. They can be
d constructed and described
by (a) the values of the
magnetic quantum number
or (b) with the axis that
defines their orientation.
f
p Orbitals
d Orbitals
f Orbitals
Phases of Orbitals
If you add up all the orbital
shapes….
You get
sphere!
