We now understand

crystal structure and how

to measure it
We now move into bigger condensed matter
questions.
First up:
What holds a crystal together? (A hot topic in early CMP)
Generalization to nonzero temps (Helmholtz free en(V,T)) gives eq. thermodynamics

Mostly electrostatics of the outer electrons,

which can describe the form of materials.
Heads up: Notes on the board won’t be available online (lots today)

Today’s Objectives
By the end of this section you should be able to:
 Use a simple harmonic oscillator model to understand
attractive forces in noble gases
 Apply a van der Waals-London interaction
 Use the Lennard-Jones potential to understand equilibrium
lattice parameters (noble gases)
 Simply by looking at the periodic table, begin to explain why
other types of bonding might exist (will develop more next
time)
Models of Atoms

K shell

L shell

M shell
 Properties by the filling of the
orbitals
1s2
1s2 2s2 2p6
1s2 2s2 2p6 3s2 3p6

Closed-
shell
elements:
noble
gases

What would you say about the properties

of noble gases?
What causes these elements to stick together?
 van der Waals Bond
 Arise from charge fluctuations graphite
in atoms due to zero-point
motion (due to Heisenberg
uncertainty principle); these
create dipole moments that are
attractive
 Depends on p2/r6, short ranged
 Typical strength of 0.2
eV/atom ~1% of other bonds
 Always present, but significant
only when other types of
bonding not possible (closed
electron shells, saturated
molecules)
 What do weak bonds mean in
terms of properties?
 Repulsive force: What works
against bringing atoms closer?

The exact dependence

with R is found
experimentally.

For inert gases ~B/R12

where the power of 12
and B found by
experiment

As atoms are brought close, the Pauli exclusion principle will

prevent two electrons from having the same quantum numbers.
Overlap increases the total energy and causes repulsive term.
Lennard-Jones Potential: joining
attractive and repulsive energies

Parameter
definitions
What about the properties of
non-noble gases?

Closed-
shell
elements:
noble
gases
 Consider the case of sodium
(atomic # 11)
 On your own write down the electronic
configuration:
1s2…
Why 4s
before 3d?
Other Properties

Closed-
shell
elements:
noble
gases

Closed-shell –plus one

(alkali) elements:
reactive due to loosely-
bound outer electron in
s-shell
Why mobile electrons appear in
some solids and not others?
 According to the very simple Drude model, the
valance electrons are responsible for the
conduction of electricity, thus termed conduction
electrons.

 Na11 ￫ 1s2 2s2 2p6 3s1 Valance electron (loosely bound)

Metallic 11Na, 12Mg and 13Al are
Core electrons
assumed to have 1, 2 and 3 mobile
electrons per atom respectively.
 This valance electron, which occupies the third
atomic shell, is the electron which is responsible
chemical properties of Na.
 What would a group I element
most easily bind with?

Closed-
shell
elements:
noble
gases
Does this group have
a valence of 7? Closed-shell–minus-one elements
(halogens): elements with high
Closed-shell –plus one electron affinity A (energy gained
(alkali) elements: when an additional electron is added to
reactive due to loosely- a neutral atom); will easily form
bound outer electron in negative ions (take additional electron)
s-shell in remaining p-shell state; very reactive
 Terminology There exist many
forms of valence!
 By valence electrons here we mean outer
electrons...the ones that could easily be
pulled from the core to form an electron gas

(In chemistry) Valence = Maximum number of

bonds formed by atom

Where would these

definitions differ?
Sometimes even the experts mix up this terminology even in papers
Organization of Periodic Table

Dmitri Mandeleev
Columns: groups with similar shells, similar properties
Rows: periods with elements with increasingly-full shells

Metallic/insulating
properties can be
understood by how loose
(i.e. low ionization energy)
outer electrons are.

So, on which side of the

table are the metals?
How the mobile electrons become mobile
 When we bring Na atoms together to form a Na
metal, the orbitals overlap slightly and the
valance electrons become no longer attached to a
particular ion, but belong to both.
+ + +

+ + +

Na metal

This is another type of bonding called metallic

bonding, stronger than van der Waals but weaker
than ionic/covalent.
 METALLIC PROPERTIES
 All conduction e-s in a metal combine to form a sea of
electrons that move freely between cores  high electrical
and thermal conductivity.
 More electrons=stronger attraction. Means melting and
boiling points are higher, and metal is stronger and harder. 
 The free electrons act as the bond (or a “glue”) between
the positive ions.
 This type of bonding is nondirectional and
rather insensitive to structure. + + +

 As a result we have a high ductility of metals:

the “bonds” do not “break” when atoms are + + +

rearranged – metals can experience a

+ + +
significant degree of plastic deformation.
 Combining alkalis and halogens

Closed-
shell
elements:
noble
gases

Closed-shell–minus-one elements
(halogens): elements with high
Closed-shell –plus one electron affinity A (energy gained
(alkali) elements: when an additional electron is added to
reactive due to loosely- a neutral atom); will easily form
bound outer electron in negative ions (take additional electron)
s-shell in remaining p-shell state; very reactive
 Electronegative and Electropositive
An atom is electronegative if it gains energy by gaining an extra electron.

What group of elements are very electronegative?

Why are the Group I elements electronegative?

What if you join Na and Cl together?

Bonding
 Elemental Na would be metallic, but you
can change that if brought in contact with
a more electronegative element (e.g. Cl)
 NaCland
Ions and Cations (salt)
Anions, Oh
My!
Draw the K, L & M shells of Na and Cl before and
after bringing in contact.

Anion = Negative ion (atom with extra electrons)

Cation = Positive ion (atom missing electrons)

Which is the anion?

Which is the cation?
Which is/are electronegative?