Lecture 4

Read textbook sections 6.3,

Friday sept. 20 - Tuesday sept. 24
6.4 1 quiz coming soon
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Ionization

Removing an electron completely from the atom.

ni = 1 ⎯  nf = 
H first ionization energy (IE1)

1
1
E = IE1 (H) = – RH 1 2 
– = RH
 2

He He has 2 e–
12
first ionization energy can’t be calculated
but it can be measured.
He+ can be calculated (and measured)
This is equivalent to He second ionization energy
(IE2), i.e. the removal of the second electron of He.

1
1
E = IE2 (He) = – RH 2 2 
– = 4 RH
 2
Quantum theory
Bohr’s model works very well for H atom and H–like
atoms  Not so well for atoms with more than 1 e–
Wave-particle duality
Removing the distinction between matter and energy,
physicists proposed that:
 Energy has mass E = mc2 (Einstein, 1905)

If energy can be particulate, can matter be wavelike?

In 1924, de Broglie suggested that the wavelength of a
particle is:
E = h  = mc2
c h h
h

= mc 2
→ m = c or  = mc apparent mass
of
photon
h
λ= , mu is the momentum (p) of the particle
mu particles of matter will display wave () and
 Small
matter (m) properties
 Evidence for the wavelike properties of matter (as
suggested by de Broglie through λ = h/p) came from
observation of diffraction patterns of electrons. (fig
6.14)
 Uncertainty principle
If an electron has both particle and wave properties,
where is it located in an atom? Heisenberg (1927)
proposed:
h
Δx∙Δp≥
4π

Instead, we specify the probability of finding an

electron somewhere in space. Describing the
electron by a wavefunction, Ψ, we relate Ψ2 to this
probability. What is the meaning of Ψ itself?
 Wavefunctions of the H atom
Instead of describing the exact position of the
electron, a wave function  is used to describe the
behavior of the electron.

 2 2
– h2 
  y2 + z2  – V = E 
2 2 +
8 2 me x
 The wavefunction Ψ is a function of 3D-coordinates,
Ψ(r, θ, ϕ), obtained by solving the Schrödinger
equation. It can be factored into a radial part, R(r),
and an angular part, Y(θ, ϕ). Wavefunctions for
single electrons are also called orbitals by chemists.

 Solving the Schrödinger equations yields several Ψ

 ψ 1s ψ 2s ψ 3s

r r r r r r
 Quantum Numbers
The state of an electron in a H atom is specified
by a set of four quantum numbers:

Quantum no. Symbol Allowed values Interpretation

governs size and energy of orbital

principle

orbital angular momentum governs type of orbital

governs orientation
magnetic of orbital

The energy depends only on n:

𝑍2
𝐸𝑛 = −𝑅𝐻 2
𝑛

Orbital shapes and energies

Orbital shapes represent the volume in which
there is
90% probability of finding the electron.
Now enumerate possible sets of quantum numbers:
n ℓ mℓ Orbital Subshell Shell
Quantum numbers
 Each e– in an atom has 4 quantum numbers associated with it.
 A wavefunction corresponding to a set of the first 3 quantum
numbers is referred to as the atomic orbital.
 Orbitals differ from each other in energy, shape and spatial
orientation of their electron cloud around the nucleus.

First quantum number, n

Principal quantum
number Principal energy
levels
n = 1, 2, 3, 4 … (integers
starting with 1)

Second quantum
number, ℓ
Also known as the angular
momentum quantum
number.
ℓ=0 s
Each
ℓ=1 principal energy level has one or more sublevels denoted by
ℓℓ.= 2 p
The
ℓ = 3general shape of the orbital is determined by ℓ
ℓℓ=is4related todn ℓ =on0, 1, (theoretical)
and so 2, …(n – 1)

Third quantum f number, mℓ

Magnetic quantum number
Determines theg spatial
direction of the electron
cloud
mℓ = – ℓ, (–ℓ + 1), …, 0, …,
 SHAPES OF HYDROGEN ORBITALS

Using right-handed coordinate axes (with the position of the label x, y, or z indicating positive
direction), sketch these orbitals in 3D-perspective. Although these are representations of 2 (which is
always positive because it means electron density), it is useful to indicate the phases of the original
unsquared wavefunction , as this will be important in later discussions of bonding. Can you locate the
radial nodes or angular nodes present in each type of orbital?

s orbitals (l = 0) z z

x x

1s 2s
p orbitals (l = 1)
z z z

x x x

2px 2py 2pz

d orbitals (l = 2)
z z z z z

x x x x x

3dxy 3dxz 3dyz 3dx2–y2 3dz2

If you find d orbitals hard to draw in perspective, you can also draw their projections onto the xy, xz,
or yz planes. Just be sure to label the axes to avoid ambiguity!
11

s orbitalsare spherical

© M. Reid, Department of Chemistry, University of Alberta (2019)

12
p orbitals have dumb bell (3D) or figure 8 (2D) shape

© M. Reid, Department of Chemistry, University of Alberta (2019)

13
d orbitals

Four orbitals have a clover leaf shape. Note their

orientation. Three (dxy, dxz and dyz) point at 45

between the axes while the fourth, dx2–y2 , points

along the axes. The fifth, dz2 , has a different shape.

Learn the shapes of all the hydrogen s, p, and d orbitals,

indicating relative phases and locating radial or angular nodes.
© M. Reid, Department of Chemistry, University of Alberta (2019)