The Quantum-Mechanical

7
Model of the Atom
 The Quantum-Mechanical
7
Model of the Atom

7.1 Quantum Mechanics: The Theory That Explains the Behavior of

the Absolutely Small

7.2 The Nature of Light

7.3 Atomic Spectroscopy and the Bohr Model

7.4 The Wave Nature of Matter: The de Broglie Wavelength, the

Uncertainty Principle, and Indeterminacy

7.5 Quantum Mechanics and the Atom

7.6 The Shapes of Atomic Orbitals

7.7 Electron Configurations: How Electrons Occupy Orbitals

 •7.1 Quantum Mechanics: The Theory That
Explains the Behaviour of the Absolutely Small

The quantum-mechanical model of the atom, a model

that explains how electrons exist in atoms and how those
electrons determine the chemical and physical properties
of elements.
• Rutherford’s version of the atom:

• Fails to explain many phenomena

 Electronic Structure Paradoxes
1. Atomic radii decrease from left to right across each row
in the periodic table.
 Electronic Structure Paradoxes
2. Rotation about single bonds occurs freely, but no
rotation is observed about double bonds.

×

 Electronic Structure Paradoxes
3. Different elements can form different numbers of bonds
•7.2 The Nature of Light

FIGURE 7.1 •Electromagnetic Radiation

 Properties of Waves

• Wavelength (λ) - distance between identical points on

successive waves
• Amplitude - vertical distance from the midline of a wave
to the peak or trough
• Frequency (ν, pronounced “nu”) - number of waves that
pass through a particular point in 1 s (Hz = 1 cycle/s)
 c
ν= c = λν
λ
FIGURE 7.2 •Wavelength and Amplitude
 FIGURE 7.4 The Color of an Object

FIGURE 7.3 Components of White Light

The Electromagnetic Spectrum

FIGURE 7.5 •The Electromagnetic Spectrum

 Properties of Waves: Interference

Constructive Interference

In phase

Destructive Interference

Out of phase
Properties of Waves: Diffraction
 Blackbody Radiation
• Classical physics fails to explain the how the emitted
radiation changes with temperature:
 Light Quanta
• Max Plank (1900) solved the problem by assuming that
energy (electromagnetic radiation) is emitted and
absorbed in discrete units, called quanta.

E = hν
Planck’s constant (h)
h = 6.63 x 10-34 J·s

• Proposes that energy can only be emitted in multiples of

hν.
 White Light
• White light is a continuous spectrum of visible light
frequencies:

Diffraction
grating

Incandescent
(“normal”)
light source
•7.3 Atomic Spectroscopy and the Bohr Model

Hg

He

H2

FIGURE 7.9 •Mercury, Helium , and Hydrogen

Emission Spectrum for Hydrogen
FIGURE 7.10 •Emission Spectra
FIGURE 7.11 •The Bohr Model and Emission Spectra
 Bohr’s Model of the Hydrogen Atom
• Electrons have specific
(quantized) energy values
• Emitted light is a result of
electrons moving from one
energy level to a lower
energy level.

1
En = -RH ( n2
)

n (principal quantum number) = 1,2,3,…

RH (Rydberg constant) = 2.18 x 10-18 J
 E = hν

E = hν

“ground state”
n=1
Predicting the Line Spectrum of Hydrogen

Ephoton = ∆E = Ef - Ei
1
ni = 3 ni = 3
Ef = -RH ( n2 )
f
1
ni = 2

nf = 2
Ei = -RH ( n2 )
i

1 1
∆E = -RH( 2 2 )
nf ni

nfnf==11
 Photoelectric Effect

• When light shines on a metal,

electrons are ejected.

• Only happens when light exceeds

some minimum threshold frequency.

• The number of electrons ejected is

proportional to the intensity of the
light, but the energy of the electrons
could not be explained.
 Photoelectric Effect
hν

• Einstein: light is made up of particles

(photons) with energy equal to hν. KE e
-

• Photons must have enough energy to

overcome binding energy (ϕ)
between e- and metal.

• Excess energy is given to the

electrons as kinetic energy (KE).
hν = KE + ϕ
KE = hν - ϕ
 Wave-Particle Duality
• De Broglie (1924): an electron, like light, behaves both as
a particles and a wave.

h v = speed of eˉ
λ = mv m = mass of eˉ

• All matter and energy shows both wave- and particle-like

properties!
→ Size determines which property dominates
MASS

Baseball Proton Electron Photon

Particle-like Wave-like
Double Slit Experiment With Electrons
Expected result Actual result
(particles) (waves!)
The Heisenberg Uncertainty Principle
 The Heisenberg Uncertainty Principle
• Heisenberg uncertainty principle
→ It is impossible to measure the exact location and the
exact speed of an electron at the same time.
→ The act of measurement changes the properties of the
electron (i.e. you can’t measure it without disturbing
it).

Where Δx and Δv are the uncertainties in the position

and velocity respectively
 •7.5 Quantum Mechanics and the Atom

orbital – a region of probability where the electron is likely to be found.

Hψ = Eψ

Hamiltonian operator Energy is the eigenvalue

wave function
 Schrödinger Wave Equation

• Describes both the particle and wave nature of the

electron in a hydrogen atom
• Solutions give energy states and their corresponding wave
functions
• Wave function (ψ, “psi”) – a mathematical representation
of an electron
→ψ2 gives a three-dimensional probability density plot
for an electron’s position in space
 Solutions to the Schrodinger
Equation for the Hydrogen Atom

Quantum Numbers
Principal quantum number: n
Angular momentum quantum number: l
Magnetic quantum number: ml
 Principal Quantum Number (n)

1
En = -2.18 x 10-18 J 2
n
n = 1, 2, 3, ….
Angular Momentum Quantum Number (l)

l = 1, 2, 3, …, n-1
Magnetic Quantum Number (ml)

ml = -l to +l
 Orbitals and Quantum Numbers
• Atomic Orbital – a three-dimensional description of the
probability density for a given wave function.

NOTE: Orbital ≠ Orbit

→ Characterized by a set of quantum numbers which

determine orbital size, energy, shape and orientation
• Four quantum numbers for each wavefunction
→ First three describe the orbital
→ Fourth describes the electron in the orbital

Ψ = f(n, l, ml, ms)

•7.6 The Shapes of Atomic Orbitals

•s Orbitals (l = 0)
probability
φ2 = probability density =
unit volume

FIGURE 7.22 •The 1s Orbital: Two Representations

FIGURE 7.23 The 1s Orbital Surface FIGURE 7.24 The Radial Distribution Function for the 1s
Orbital
 The nodes in quantum-mechanical atomic orbitals are three-dimensional analogs of the nodes on a
vibrating string.
FIGURE 7.25 •Probability Densities and Radial Distribution Functions for
the 2s and 3s Orbitals
 p Orbitals ( l = 1 )

FIGURE 7.26 (a) The 2p Orbitals and, (b) the Radial

Distribution Functions for the 2p and 3p Orbitals

FIGURE
 d Orbitals ( l = 2 )

FIGURE 7.27 •The 3d Orbitals

The Phase of Orbitals
 f Orbitals ( l = 3 )

FIGURE
FIGURE 7.28 •The 4f Orbitals
Hydrogen-Like Wave Functions
TABLE 7.1 Solutions to the Schrödinger Equation (wave functions) for a One-Electron Atom
 3/2 –Zr/a0
Z
R(1s) = 2 e
a0
cannot have value of 0

constant exponential

Z 3/2 Zr –Zr/2a0
1
R(2s) = 2– e has value of 0 when
80 a0 a0
2a0
r =
st Z
1 -order
constant exponential
polynomial
•7.7 Electron Configurations
or How Electrons Occupy Orbitals
•Electron Spin and the Pauli Exclusion Principle

1
H 1s

H H

ms = + ½ ms = + ½
FIGURE 7.30 •Stern-Gerlach Experiment
 2
He 1s

Pauli Exclusion Principle: No two electrons in an atom can have the same four quantum numbers
Sublevel Energy Splitting in Multielectron Atoms

Degenerate Orbitals: Orbitals of the same energy (ex. 3s, 3p, 3d).

Multi-electron atoms:

Es < Ep < Ed < Ef

Coulombs Law:
1 q1q2
E=
4πε0 r
FIGURE 7.31 •Shielding
 FIGURE 7.32 Radial Distribution Functions for FIGURE 7.33 Radial Distribution Functions for the 3s, 3p, and 3d
the 1s, 2s, and 2p Orbitals Orbitals
FIGURE 7.35 •Change in the energy ordering of orbitals from a one-electron
atom (like hydrogen) to a multielectron atom.
Electron Configurations for Multielectron Atoms

Electron configuration Orbital Diagram

2 1
Li 1s 2s

1s 2s

2 2 2
C 1s 2s 2p

1s 2s 2p
 -
- e
Symbol #e config Orbital Diagram

2 1
Li 3 1s 2s

1s 2s 2p

2 2
Be 4 1s 2s

1s 2s 2p

2 2 1
B 5 1s 2s 2p

1s 2s 2p

2 2 2
C 6 1s 2s 2p

1s 2s 2p
 -
- e
Symbol #e config Orbital Diagram

2 3
N 3 1s 2s

1s 2s 2p

2 4
O 4 1s 2s

1s 2s 2p

2 2 5
F 5 1s 2s 2p

1s 2s 2p

2 2 6
Ne 6 1s 2s 2p

1s 2s 2p
 4s 3d 4s 3d

Sc Fe

Ti Co

V Ni

Cr Cu

Mn Zn
 When writing the electron configuration of a transition metal cation, remove the electrons
in the highest n-value orbitals first, even if this does not correspond to the reverse order of
filling .

4s 3d

2+
V
Paramagnetic: unpaired electrons generate a magnetic field and are attracted to an external
magnetic field.

5s 4d

Ag

Diamagnetic: paired electrons do not generate a magnetic field and are slightly repelled by an external
magnetic field.

4s 3d

Zn

2+
Zn
A few questions…

Correct quantum numbers for 4f sublevel?

What is the value of the angular momentum l for 3p?

Is the following combination of quantum numbers possible?

n = 2, l = -1, ml = 1
n = 4, l = 0, ml = 0
n = 3, l = 2, ml = 2

Which of the following are possible: 3d, 2p, 4d, 3f, 5d

 Learning Objectives
• Apply the properties of waves to electromagnetic
radiation and convert between frequency, speed,
wavelength
• Relate the energy of light quanta to its frequency and/or
wavelength
• Interpret atomic emission spectra in terms of the Bohr
theory of the atom; calculate energies of emitted light for
given transitions (and vise versa)
• Relate the wave-like and particle-like properties of matter
using the De Broglie equation
• Derive the 3-dimensional shape of an atomic orbital given
its corresponding quantum numbers (and vise versa)