Soft Condensed Matter

PH4063

Lecture 2:
Forces in soft matter systems

For a detailed account:

J. Israelachvili, Intermolecular and surface forces, Associate Press
 Why do we care?
The intermolecular forces determine most of the properties of
materials, including their

Liquids: Viscosity Solid: Elastic properties

How does it flow? How does it deform?

Viscoelastic materials:
Deform and flow.
It depends on the observation timescale
 Overview
The physical force that dominates the behavior of soft matter systems
is the electrostatic interaction. Marginally, gravity could also be
relevant.

In this lecture:
Electrostatic interaction: very short recap

Electrostatic interaction:
Between atoms: close and/or distant
Between molecules
Between macroscopic objects
Electrostatic interaction
 Coulomb interaction
The electrostatic interaction energy between two electric charges
1 and 2 placed at a distance , in void, is:

1 1 2
12 =
40 12

We can say that an electric charge generates an electrostatic

1
potential = , and that the energy of interaction of a charge
4
at a distance from charge is = .
 Linearity of interaction
The electrostatic interaction is linear.

If there are many charges, , located in positons , the electrostatic

potential in position is the sum of the potentials generated by the
single charges
1
=
4

Similarly, if the charge can be assumed as continuously distributed in a

body, with charge density ( is the total charge in volume ),
the electrostatic potential generated by the body is
1
= 0
4 0 0
Where the integral is over the volume containing the charges.
 Electrostatic force
The electrostatic force acting between two charges is simply derived
from their interaction energy as
1 1 2
= = , , = 2
40 12

The force is attractive is 1 2 < 0, repulsive otherwise.

Since the electrostatic interaction energy is = 2 , the force can be

also expressed as = 2 , where = is the electric field.
 Recap: electric dipole
An electric dipole is defined as a collection of two charges of opposite
sign, placed at a distance . The term dipole is used when the effect of
these two charges is considered at distance from them, with .

A dipole is indicated with a vector = , that conventionally points

towards the positive charge.

= is known as dipole moment.

Dipole are relevant to us as most molecules are little dipoles.

 Recap: dipole in a field

 Recap: dipole in a field
Suppose we have a dipole in an electric field . What is the force
acting on it? It is convenient to consider that the electric field is the
gradient of an electric potential. The overall dipole energy is
1 1
= + +

2 2
Assuming the field to vary slightly over the length scale of the dipole,
we can Taylor expand the potential, writing
1 1

+ = +
2 2
and
1 1
=
2 2
So that:
= = = cos
 Recap: dipole in a filed
So that:
1 1 1

= = = cos
2 2 2

The energy is minimal when cos = 1, i.e. = 0. The dipole

experiences a torque that aligns it parallel to the electric field.
 Dipole-dipole interaction
The interaction between two dipoles is known as the dipole-dipole
interaction. We just give the expression, for dipoles separated by a
distance which is much larger than their size:

Remember: dipole-dipole interaction is attractive, and varies as 3

 Interaction in a medium
The electrostatic interaction between two charges in a medium
differ from that of the two charges in void.

The reason is that the medium, a collection of atoms and/or

molecules, can be seen as a collection of dipoles (existing or
induced by the filed). In general, the dipoles are randomly oriented
and do not exert any net force on a charge.

In the presence of a charge, the dipoles align to the field this charge
generates. This effect is known as polarization. Two charges in a
medium, therefore, are surrounded by dipoles that are not randomly
oriented.

This leads to a reduction of the effective electrostatic interaction

between the charges.
 Interaction in a medium

Atom or non-polar molecules

in an electric field E:
1) The field create the dipoles
2) The field align the dipoles

Polar molecules (dielectric) in

an electric field E:
1) The field align the dipoles
 Permittivity
This effect is simply described, from a mathematical point of view,
via the introduction of the relative permittivity, .

The interaction energy in a medium with electrical permittivity is

1 1 2
12 =
40 12

= 0 is the absolute permittivity of the medium.

For water, 80. Thus, water strongly reduces the electrostatic

interaction. As we will see, this reduction is the basis of dissolution
(e.g., of salt in water).
Atoms and their interactions
 Hydrogen atom
The hydrogen atom is composed by a proton (p) and by an electron (e).
In a classical picture, the electron is described as revolving around the
proton. In QM, a wave function is associated to each particle, (),
and the probability to observe a particle in is = 2

The masses are:

1.6 1027 Kg and 9.1 1031 Kg.
( e revolves around p, and not vice versa).

The charges are

= = 1.6 1019 C
=

The radius, known as Bohrs radius, is:

0 = 5.29 1011 m
 Forces
1. Electrostatic interaction:

1 ()
0 = 13.6
4 0
[1 = 1.6 1019 J]

2. Quantum mechanical repulsion:

The electrostatic interaction is attractive, as it decreases with the

interparticle separation (0 ). Proton and electron tend to collapse.
The collapse is prevented by a short range repulsion of quantum
mechanical origin.
 Generic atoms
In general, atom contains and electrons.
The forces at work include
1. Electrostatic interaction:
repulsive between all couples of electrons
repulsive between all couples of protons
attractive between all proton-electron pairs

2. Quantum mechanical repulsion

Practically, the repulsive quantum mechanical interaction
depends on the electronic status (Z) of the atoms. It is
always there for noble gas, or full valence shells.

We have no time to see this detail, but you should have seen them
in your chemistry classes.
 The periodic table
One electron in valence shell Full valence shell
One electron missing

Two electrons missing

Four electrons missing

Short-range interaction between two atoms
When two atoms are at a distance comparable to their size, their
interaction is determined by their electronic configurations.
There are two possibilities:
1. Strong repulsion
atoms are stable and repel as hard spheres

2. Strong attraction covalent bond

atoms attract. In this case the atoms share some electrons,
and form a molecule. Example:

Hydrogen molecule Lithium fluoride

 Covalent bond
A covalent bond occurs when two atoms share two electrons. The
energy scale is 100. This means that covalent bonds do not
break because of thermal fluctuations.

In soft matter, covalent bonds can be considered as permanent

bonds.

Covalent bonds are sometime called chemical bonds.

 Notation
Covalent bonds are indicated with a dash (-)
H H H2: Hydrogen

H H
H2O: water
O

Polyethylene

Subsequent monomers of a polymer are connected via covalent bonds

 Further examples
In a standard covalent bond, two protons share two electrons.
H H H2: Hydrogen

Is it also possible that four protons, two for each atom, share four
electron. In this case one has a double covalent bond. Examples:

O O O2: Oxygen

The main feature of a covalent bond is the sharing of electrons between

different atoms. The electron are delocalized. Covalent bonds lead to a
small electrical resistivity.
 Metallic bond
In a covalent bond, two protons share two electrons,

Metallic bonds are the extension of covalent bonds to system

comprising many atoms. Thus, in a metallic bond N protons share N
electrons.

The electrons are in a delocalized cloud, assuring a low electrical

conductivity.

+ + + +

+ + + +
Cloud of delocalized
+ + + + electrons
+ + + +
 Dipoles
If the atoms forming the bonds are equal, then the
center of mass of the protons, and that of the electrons,
are the same. Thus, = 0 and there is no dipole.
2 , 2 , ..

If the atoms forming the bonds differ, the center of

mass of the protons and that of the electrons differ, and
> 0. The value of depends on how the electrons are
shared.
, , ..
Dipole values of molecules are tabulated.
 Ionic bond
When a two atoms for a covalent bond, the sharing of the electrons
could be heavily unbalanced. That is, instead of saying that the two
atoms share an electron, we say that an atoms loses an electron,
and the other one receives an electron.

When this is the case, the atoms form an extremely unbalanced

covalent bond, which is known as ionic bond.
Ionic = unbalanced covalent bond

To indicate the
formation of a ionic
bond, the following
notation is used:

Sodium, Na Chlorine, Na
+ -e
e
 Ionic interaction
One electron in valence shell Full valence shell
One electron missing

Two electrons missing

Four electrons missing

Ionic bonds = unbalanced covalent bond
A typical example is sodium chloride the usual table salt.

Na electronic configuration: full shell + 1 electron

Cl electronic configuration: full shell 1 electron

 Ionic interaction energy
The energy scale of ionic bonds can be computed the transfer of an
electron, or more generally of a charge q.
Because of this transfer, the two atoms, with no initial net charge,
will acquire a charge +q and -q, respectively.
1 1
The interaction energy is therefore = <0
4 0
Order of magnitude [q = electron charge; r = atom size]

10 1020 100
Interaction energy strongly reduced in solution; will see

Ionic bonds lead to the formation of molecules with a

dipole.
Long-range interaction between two atoms
The interaction between two atoms A & B far apart is the
interaction between two systems made of a positive charge, the
protons, surrounded by negative charges, the electrons.

Suppose that, by fluctuation, atom A develops a transient dipole.

This dipole generates an electric field, that polarizes atom B.

Thus, A & B interact as two dipoles, but the dipole of B is induced

by A. The resulting interaction is known as the
van der Waals interaction:

= 6

 Van der Waals interaction
The interaction is attractive.

The energy scale is E ~ 10-20J, comparable to kBT ~ 10-21 J.

Since E ~ kT, atoms do not generally condense because of this
interaction.

The interaction scales as 6 .

This is because we have a dipole-dipole interaction
1 2
3
In which dipole 2 is induced by dipole 1 . Since the magnitude of
an induced dipole is proportional to u2 3 , we recover the 6
dependence.
Interaction between molecules
 Polar and non-polar molecules
Molecules result from the bonding of atoms.

We have seen that the formation of a bond might lead to the

formation of molecules with or without an electric dipoles.

Molecules without an electric dipoles are known as

Non-polar molecules
2 , 2 , ..

Molecules with an electric dipole are known as:

Polar molecules.
The dipole moment of polar molecules is tabulated.
, , ..
Long-range interaction between non-polar
molecules
When observed from far away, there is not much difference
between a non-polar molecule and an atom.

In both cases we have a collection of protons and of electrons, that

share the same center of mass.

The interaction between two non-polar molecules is therefore

analogous to that of two atoms, i.e. the van der Waals interaction:

= 6

Long-range interaction between polar
molecules
Two polar molecules, when far away, interact as two dipoles.
The interaction energy is therefore

= 3

 Interaction between distant molecules
Both the dipole-dipole potential and the van der Waals interaction
1) Are approximations working for distant objects
2) Are attractive

The two interactions have a different functional dependence.

V(R)

R-3
R-6
 Hydrogen bond
Ionic molecules have a dipole, and therefore interact via a dipole-
dipole potential when at long distances.

In some cases, when the distance between two ionic molecule is

small, the electromagnetic interaction leads to the emergence of a
new kind of bonds, known as hydrogen bond.
 Hydrogen bond
Hydrogen bonds are interaction that arises between electronegative
atoms such as O-, N- and F- and the electropositive H+.
Consider the interaction between two polar molecules, A-B+ and C-D+.
These molecules are two dipoles, so we have a dipole-dipole interaction.
A- B+ C- D+

If B = Hydrogen, its size is particularly small. The two molecules can be

quite close, and the dipole approximation breaks down. The resulting
interaction could between H+ and C- is unusually large and directional, and it
known as hydrogen bond.

A- C- D+
H+
 Hydrogen bond
The hydrogen bonds is indicate with
For instance, A-H C-D, indicates the presence of an H-bond between
H and C.

Hydrogen bonds are strong and directional, so that they can orientate close
molecules in liquids. A typical example is water:

Strength: 5-10 kBT

 Boiling temperature
When a liquid boils, molecule on the surface detach and enter the gas
phase. How much energy is needed?

The energy needed is the energy required to detach a molecule in the

liquid from its close molecule, and is therefore related to the molecule-
molecule interaction.

In the presence of ionic bonds, the attractive interaction between

different molecules is particularly strong, so the energy required is
particularly high. That is, the boiling temperature is high.

For instance, water (ionic) boils at 100 .

For comparison: methanol (66C), alcohol (78C), ammonia (-33C).

Short-range interaction between molecules

When close to each other two molecules interact though a strong

repulsive force, as two stable atoms.

There is not a close form for the dependence of the energy on the
distance.

The properties of a system does not depend strongly on this

repulsive force, as long as the repulsion is strong, as molecules
and atoms are impenetrable.

The most common model assumes the interaction energy to

increase as 12 as the distance between the molecules

decreases.
 Lennard-Jones potential
The most popular model for the interaction between two atoms.
Is it really good for full valence shell atoms (noble gases).
It is not good for polar molecules.

V(r) Model: Lennard-Jones potential

12 6
() = 4

r
 Recap
In all cases, we are dealing with electromagnetic interaction

Interaction Energy scale

- van der Waals interaction kBT
Distant molecules
- Dipole-dipole interaction kBT

- Covalent bonds 100 kBT

- Metallic bonds 100 kBT

- Ionic interaction 100 kBT

- Hydrogen bonds 5-10 kBT

 Is gravity relevant ?
Exercise:
Is gravity relevant for a system of aluminum (r = 3x103 Kg/m3)
particles of diameter D at ambient temperature T = 300K ?

We compare the thermal and the gravitational energy scales:

Thermal energy scale: ET = kBT = 4x10-21 J
Gravitational energy scale: EG = mgD ~ rD3gD = rgD4

D = 1nm EG ~ rgD4 ~ 3x104 (10-9)4 ~ 3 10-36J << ET

D = 1mm EG ~ rgD4 ~ 3x104 (10-6)4 ~ 3 10-20J ~ ET

D = 1mm EG ~ rgD4 ~ 3x104 (10-3)4 ~ 3 10-16J >> ET

 Gravity in soft-matter systems
- gravity is not relevant for atomic particles:
L ~ 1nm

- gravity might be relevant for colloidal particles:

L 1mm

- gravity is relevant for granular particles:

L > 1mm

Gravity might be relevant

 Hydrophobic effect
Consider the interaction of water we other molecules

Water molecules form strong H bonds among them. If a non-polar (no

dipole) molecule is inserted into water, some H bonds are lost, which cost
energy.

Shortly: water aims at reducing the surface contact area with non-polar
molecules. In the presence of many non-polar molecules, the surface
contact are is minimized when these molecules are packed together.

A typical example is oil, which in non-polar, and thus not soluble in water.
 Interaction between macroscopic objects
Consider two objects A & B.

Objects A is made of atoms, that are in position , = 1, ,

Objects B is made of atoms, that are in position , = 1, ,

The energy of interaction between A and B is the sum of the energy of

interaction of every atom of A, with every atom of B.

If () is the energy of interaction between any two atoms of A & B, the

total energy of interaction is

=
=1 =1
 Interaction between macroscopic objects
Since the interaction between atoms is attractive, the interaction
between macroscopic objects is also attractive.

Thus, two colloidal particles attract each other.

The overall interaction energy depends on the size and shape of the
materials, as well as on their atomic number density (number of atoms
per unit volume).

We will consider simple cases in the next lesson.

 L2 - End
Next lesson: tutorial

Exercises related to the computation of the interaction

between molecules and large objects.