CHAPTER 8

Atomic Physics
 Allowed solutions to Schrödinger equation for two non-
interacting particles accounting for their indistinguishable
property

 Bosons and fermions, Pauli’s exclusion principle again

 8.1 Atomic Structure and the Periodic Table

What distinguished Mendeleev was not only genius, but a
passion for the elements. They became his personal friends; he
knew every quirk and detail of their behavior.

- J. Bronowski

Suffices for this chapter, derived results are

numerically nearly correct, also we do allow
for an inclusion of effects of the fourth
dimension (by multiplying what goes on in
3D with the spin wave function) 1
 A consequence of the uncertainty principle

There is no path for a quantum mechanical object to follow, uncertainty

2
principle forbids this
 But without spin,
so it is not really
convincing
if But this is not reasonable !

Could also have two parts: L1 and L2

If that made sense, the
particle that we could find at x
= ½ L needed to be always
the one in state n = 1 (the
other particle has zero
1 2 even if only one part probability there), if we were
to change labels the same
condition would apply - so we
would violate the condition
that quantum mechanical
particles are indistinguishable
as a consequence of the
uncertainly principle, so it
cannot make sense

3
 Two basis types of particles,
bosons (integer spin) and
fermions, (half integer spin)
When n = m for both particles, wavefunction = zero

they are fermions

Matter is composed of fermions, half integer spin,

Paraphrasing Winston Churchill: not everybody at the horse races is a crook, but all the crooks are at the
horse races: Not all bosons are force particles, but all force particles are bosons 4
 Pauli Exclusion Principle
 To make sense of atomic spectroscopic data of the anomalous
Zeeman effect, Pauli proposed his famous exclusion principle:
No two electrons in an atom can have the same set of
quantum numbers (n, ℓ, mℓ, ms).

 It applies to all particles of half-integer spin, which are called

fermions, electrons and composite particles (protons and
neutrons) in the nucleus are fermions. Each of the latter (composite)
particles is composed of three quarks – which are also fermions, spins add up,
so no chance for them to become a boson)

The whole periodic table (chemical properties) can be

understood by two rules on the basis of the hydrogen atom:
1) The electrons in an atom tend to occupy the lowest energy levels
available to them.
2) Pauli exclusion principle.
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Hydrogen atom model, Schrödinger plus spin

The principle quantum number has letter codes.

n= 1 2 3 4 ..
Letter = K L M N …

n = shells (e.g.: K shell, L shell, etc.)

n and l together for subshells (e.g.: 1s, 2p, 3d – where leading

number refers to principal quantum number

in each hydrogen-analogous orbital (3D spatial

wavefunction-squared) there can only be up to two
electrons with opposite spin

6
 Number of sub-shells of each type (2ℓ + 1)
Since n = 3, M shell L K
three sub-
shell shell
shell types,
first is called 1
3s (l = 0), 1
second 3p (l 1
= 1), and third
3d (l = 2), 18 Since l
electrons = 0, just
max when all one sub
9 sub-shells shell
are filled called s

3
3
Since n = 2, two sub-
shell types, one is
5 called s (l = 0) the other
p (l = 1), 8 electrons
max in this shell when
all 4 sub-shells are filled

Filled and half-filled shells and sub-shells result in spherical symmetric electron 7
density distributions for the corresponding atoms, (Unsoeld’s theorem)
 Atomic Structure
Hydrogen: (n, ℓ, mℓ, ms) = (1, 0, 0, ±½) in ground state. Both spin states
with same probability
 In the absence of a magnetic field (and ignoring hyper-fine structure
and spin orbit coupling), the state ms = ½ would be degenerate with the
ms = −½ state. (different wavefunction but same energy)
Helium: (1, 0, 0, ½) for the first electron, (1, 0, 0, −½) for the second
electron.
 Electrons have anti-aligned (ms = +½ and ms = −½) spins, they are
being paired and spins cancel, total spin becomes an integer (0), i.e.
the whole particle becomes a boson, composed of fermions (which are
subject to the Pauli exclusion principle, nuclear spins cancel also,
happens at there are two protons and two neutrons).

Electrons for H and He atoms are in There is no sub-shells at all for n =

the K shell. 1, because l = 0, meaning ml also =
H: 1s He+: 1s1 just like H 0, so just one set with spatial (3D)
He: 1s2 Li++: 1s1 just like H quantum numbers (1, 0, 0, ±½)

Number of sub-shells is number of sets with unique spatial (3D) quantum numbers 8
 Hund’s rule, rather than
joining an orbital that is
already occupied by one
electron, the next
electron goes into an
orbital all by itself to
minimize total energy

different hybridizations in
crystals

Ammonia, NH3

H20

Ne
9
 Atomic Structure
How many electrons may be in each shell and subshell?
apparent irregularities
Total
For each mℓ: two values of ms 2
For each ℓ: (2ℓ + 1) values of mℓ 2(2ℓ + 1)

Recall: ℓ = 0 1 2 3 4 5 …
letter = s p d f g h …
ℓ = 0, (s state) can have two electrons.
ℓ = 1, (p state) can have six electrons, and so on.

Multiple electrons will interact

Electrons with higher ℓ values are less shielded from the
nuclear charge and have higher energy levels than those with
lower ℓ values. They have also a larger angular momentum.
4s fills before 3d – it’s due to interactions between the
electrons, extra potential energy terms in the Hamiltonian
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 11
Note the closed subshells for any n at the noble gasses
Note the closed subshells for any n at the noble gasses

Last of
the stable
elements

Occur only in U-
ores and nuclear
reactors

Do not
occur
naturally
on Earth
Lr

12
 misleading

no Z =
119 yet
and
beyond

Element 120 Roentgenium, Z = 111

would have misleading
8s2
14 boxes each
13
 whenever [ ] around atomic mass, radioactive
correct

Needs updating for names and discoveries, Un.

15 boxes each

Standard long periodic table, Y and Lu have an analogous electronic

14
structure for outer electrons
 15
15 boxes each??, f means l = 3, max. number of electrons in f-sub-shell 2(2 l + 1) = 14
 #56 La #72
Ac
Lutetium belongs to the lanthanides? Nope

only 14 Lu
boxes
Lr
each !!!

There are 14 = 2(6+1) f-boxes, but both Ce and Th just start with one electron in the
boxes of the d-block, so it is not obvious if La should be in the same column as Sc
and Y, or if Lu and Lr should be in the same column as these two. Actually it is Lu
(Lutetium) and Lr (Lawrencium).
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Note that La is #57, Lu is # 71 and its next neighbor is Hf with #72
 Number of sub-shells
of each type (2ℓ + 1)

note that the f-block is just 14

boxes long, in it the seven f-sub-
shells for n = 3 and 4 get filled up,
this is achieved when we come to
Yb and No, then this block ends

No question marks, this is the more systematic way to show the periodic table
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18
Groups and Periods in Periodic Table
Groups:
 Vertical columns.

 Same number of electrons in the ℓ orbits.

 Can form similar chemical bonds as these are determined by the outermost
(most loosely bound) electrons
Periods: all atoms have about
the same size
 Horizontal rows.

 Correspond to filling of the sub-shells.

 Beginning of each period shows in atomic radii plot, end of each period
shows more or less in ionization energy.

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 32 = 14 + 10 + 6 + 2

18 = 10 + 6 + 2

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 The Periodic Table
Inert Gases:
 Last column of the periodic table

 Closed p sub-shell except helium (which has closed s sub-shell)

 Zero net electronic spin and large ionization energy

 Their atoms interact only very weakly with each other, mono-atomic gasses

Alkalis:
 Single s electron outside an inner core, largest atomic radii

 Easily form positive ions with a charge +1e, highly reactive

 Lowest ionization energies

 Form chemical compounds with valence number 1, e.g. Li2O (lithia, 8 Li

cations and 4 O anions per unit cell of a crystal), for molecules: H2O
 Electrical conductivity in metals is good as the electron joins the free
electron cloud easily
Alkaline Earths:
 Two s electrons in outer sub-shell

 In chemical compounds with valence number 2, e.g. MgO

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(magnesia), 4 Mg + 4 O per unit cell of a crystal
The Periodic Table
Halogens:
 Need just one more shared electron to fill outermost subshell

 Form strong ionic bonds with the alkalis, e.g. NaCl

 More stable configurations occur when p subshell is completely

filled, therefore highly reactive

Transition Metals:
 Three rows of elements in which the 3d, 4d, and 5d are being filled

 Properties primarily determined by the s and p electrons, rather

than by the d subshell being filled, which are further inside the
atoms
 Initially d-shell electrons with unpaired spins, Hund’s rule, cause of
ferromagnetism
 As the d subshell is filled further, the magnetic moments, and the
tendency for neighboring atoms to align spins are reduced 22
The Periodic Table
Lanthanides (rare earths), starts with La
 Have the outermost 6s2 sub-shell completed

 As also occurs in the 3d sub-shell, the electrons in the 4f sub-shell

prefer unpaired electrons (Hund’s rule) contribute to ferromagnetic
effects

Actinides: (all radioactive), starts with Ac

Inner sub-shells are being filled while the 7s2 sub-shell is completed
 Difficult to obtain chemical data because they are all radioactive
(last stable atom is Bi, # 83)
 Commercial usage of U, Pu, Am

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Summary
Physical
foundations
are electronic
structures
their
consequences
are all of
chemistry !!!

All atoms in crystals are of about the same size, 0.1 – 0.5 nm diameter, in fact, their
size is inferred on how much space they take up in crystals

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missing in nature
 Periodic physical and chemical properties of atoms are due to periodic electronic
structures, chemical properties depend strongly on the outermost electrons,
ferromagnetic properties are due to unpaired spins in d and f orbitals (Hund’s rule)

Th
13.6

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Fermions have spin ½

spin 0, large
mass, charge 0

spin 2, mass 0,
charge 0
proton: two up one down quark, spin ½
neutron: one up two down quark, spin ½ Bosons have integer spin, 0, 1, 2
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