Atomic Structure
and Periodic Table
Chapter 2; Miessler
Chapter 1; Housecroft
Chapter 1; Douglas
1
2
Experiment Results
Hypotheses
Laws
Theories & Models
D- Chapter 1 p4 3
M-Chapter 2 p10 4
M-Chapter 2 p17
5
Before Understanding Quantum Chemistry
1. Dalton’s Atomic Theory.
2. Cathode Ray.
3. Determine the Magnitude of the Electron Charge
by Milliken’s Work.
4. The Metal Foil Experiment of Rutherford’s Work.
5. The Photoelectric Effect.
6. The Bohr Model.
7. The Matter Wave.
8. The Uncertainty Principle 6
The emission spectrum of hydrogen
Figure 1.2
A schematic representation of part of the emission spectrum of hydrogen showing the
Lyman, Balmer and Paschen series of emission lines. The photograph shows the
predominant lines in the observed, visible part of the spectrum of hydrogen which appear
at 656.3 (red), 486.1 (cyan) and 434.0 nm (blue). Other fainter lines are not visible in this
photograph
H-Chapter 1 p5-6
Bohr’s Theory
1 1
E = RH 2 − 2
nl nh
−2 2 me Z 2 e 4
R=
h2
when Z = 1 for hydrogen atom
R = 13.6eV or 109680 cm -1
Rydberg constant or 1312kJ
D-Chapter 1 p10-11
M-Chapter 2 p12-13
H-Chapter 1 p5-6
9
The Particle in A Box
−h 2 2 ( x )
2 = E ( x )
8 m x
2
V =0
= A sin rx
2 n x
= sin
a a
M-Chapter 2 p15-17
10
The Schrödinger Equation
kinetic energy potential energy
^
H = E
−h 2 2 2 2
2 2 + 2 + 2 + V ( x, y , z ) ( x, y , z ) = E ( x, y , z )
8 m x y z
− Ze 2 − Ze 2
V= =
4 o r 4 o x 2 + y 2 + z 2
M-Chapter 2 p15-17
11
M-Chapter 2 p17-20
12
M-Chapter 2 p17-20
13
M-Chapter 2 p17-20
14
M-Chapter 2 p17-20
15
M-Chapter 2 p17-20
16
M-Chapter 2 p17-20
17
Spherical Coordinates
( r, , )
= R ( r )( ) ( )
radial function
angular function
M-Chapter 2 p17-20
18
x = rsincos
y = rsinsin
z= rcos
H-Chapter 1 p9
Definition of the polar coordinates (r, , ) for a point
Figure 1.4
shown here in pink; r is the radial coordinate and and
are angular coordinates. and are measured in radians
(rad). Cartesian axes (x, y and z) are also shown.
20
M-Chapter 2 p21-22
21
M-Chapter 2 p21-22
D-Chapter 1 p19 22
Radial distribution functions, 4 r2R(r)2, for the 1s, 2s
Figure 1.7
and 3s atomic
H-Chapter 1 p12-13
orbitals of the hydrogen atom.
Radial distribution functions, 4r2R(r)2, for the 3s,
Figure 1.8
3p and 3d atomic orbitals of the hydrogen atom.
H-Chapter 1 p12-13
y
D-Chapter 1 p20
x = rsincos
y = rsinsin
z= rcos
25
M-Chapter 2 p21-22
26
M-Chapter 2 p21-22
27
M-Chapter 2 p21-22
28
D-Chapter 1 p21 29
M-Chapter 2 p23
30
M-Chapter 2 p24
31
M-Chapter 2 p24
32
H-Chapter 1 p13-15
Boundary surfaces for the angular parts of the 1s and
Figure 1.9
2p atomic orbitals of the hydrogen atom. The nodal plane
shown in grey for the 2pz atomic orbital lies in the xy plane.
H-Chapter 1 p13-15
Representations of
Figure 1.10
an s and a set of three
degenerate p atomic
orbitals. The lobes of the
px orbital are elongated
like those of the py and pz
but are directed along the
axis that passes through
the plane of the paper.
The figure shows ‘cartoon’
diagrams of the orbitals
alongside more realistic
representations generated
using the program Orbital
Viewer (David Manthey,
Cross-sections through the (a) 1s (no radial nodes),
Figure 1.11
(b) 2s (one radial node), (c) 3s (two radial nodes), (d) 2p (no
radial nodes) and (e) 3p (one radial node) atomic orbitals of
hydrogen. The orbitals have been generated using the
program Orbital Viewer (David Manthey,
www.orbitals.com/orb/index.html). H-Chapter 1 p13-15
Representations of a set of five degenerate d
Figure 1.12
atomic orbitals. The orbitals have been generated
using the program Orbital Viewer (David Manthey,
www.orbitals.com/orb/index.html). H-Chapter 1 p13-15
H-Chapter 1 p16
D-Chapter 1 p32-33 37
D-Chapter 1 p25
38
Aufbau Principle-Klechkowski rule.
(building-up principle)
1. Electrons are placed in orbitals to give the lowest
total energy to the atom.
2. Pauli exclusion principle.
3. Hund’s rule of maximum multiplicity.
Huheey-Chapter 1 p17-20
4. Klechkowski rule. M-Chapter 2 p 26-30
D-Chapter 1 p 24-27 39
Chapter 2 Huheey
40
The core electrons shield valence electrons
from the nuclear charge valence electrons
core electrons
H-Chapter 1 p24
1. Exchange energy, Pe (negative)
2. Coulombic energy of repulsion, Pc
(positive)
Give example and see page 26~29 (Miessler)
42
M-Chapter 2 p26-28
43
+
M-Chapter 2 p26-28
44
M-Chapter 2 p26-28
45
M-Chapter 2 p29
46
M-Chapter 2 p32
47
M-Chapter 2 p34-35 48
Potential Energy
M-Chapter 2 p34-35
49
Potential Energy
M-Chapter 2 p34-35
50
Effective Nuclear Charge (Z*)
1. Z* = Z – S
Z = nuclear charge, S = shielding constant
Empirical Slater Rules for S
2. Find electron configuration of the atom (ion)
3. Electrons in higher group do not shield those in
lower group.
4. For ns and np group electrons:
a. a shielding of 0.35 is contributed by each other
electron in the same group. D-Chapter 1 p40
M-Chapter 2 p30
51
Huheey-Chapter 1 p18-20
b. except for 1s electron, which contributes 0.30 to
the shielding of the other 1s electron
c. electrons in n-1 group contribute 0.85
d. electrons in n-2 group contribute 1.0
5. For electrons in nf and nd group:
a. electrons in the same nf and nd group contribute
0.35.
b. electrons in the left group contribute 1.0.
6. Energy of electron in atom:
−( Z *)2
E= 2
(13.6eV )
n
52
Exercise 2.3 of M-Chapter 2 p32
An example D-Chapter 1 p41
53
Ionization Energy
Electron Affinities
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Z* (4s) 3 3.15 3.3 2.95 3.6 3.75 3.9 4.05 3.75 4.35
Z* (3d) 3 3.65 4.3 4.6 5.6 6.25 6.9 7.55 7.85 8.85
Chapter 2 p37
54
Ionization Energy and Electron
Affinity
A (g) → A +1( g ) + e − ΔH ionization energy, IE
A +1(g) → A (g) +e- ΔH -(ionization energy), -(IE)
−
A-( g ) → A (g) + e ΔH electron affinity, EA
−
A (g) + e → A -
(g) ΔH -(electron affinity), -(EA)
D-Chapter 1 p42~46
M-Chapter 2 p37~38
55
Chapter 2 p38
56
Electron Affinities
D-Chapter 1 p48
57
M-Chapter 2 p39
58
Chapter 2 p39
59
Why ?
M-Chapter 2 p40
60
Why ?
M-Chapter 2 p40
61
Why ?
M-Chapter 2 p47
62
