Notes on Microphysics

1. Introduction
We live in a world that is composed of elements. We are large, say, relatively. So we define our
world as macro world, even though we are micro in the eye of galaxy or even the earth they
are macro also. We will speak about the micro world, the world smaller then we normally
regard. The micro world, however, is nothing strange. It is just part of our world at which we
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are looking smaller scale. Thus comes the scale. We have micro robots of several cm , they
are still quite large in the context we are discussing, the difference of physical phenomenon is
not very much different. However, when the scale is continuously getting down, we will see
the capillary phenomenon - liquid level in a small capillary vessel could be high than the level
outside of it. Continuously going down, van der Waals force, electric static force and surface

FIGURE 1. The Scale

tension play more and more important roles in the determination the behaviours of microscopic
things. In the mean while, inertial force, gravitational force become less dominant. Those
changes of dominant physical quantities between different scales is called scaling effect.

FIGURE 2. Scaling effect

FIGURE 3. Scaling effect in micromanipulation.

The scaling effect makes the micro world different from the macro world we get used to. For
an example shown in Fig. 3, grasping an object and releasing it, an operation we do many time
a day, could be difficult in the micro world - the object is difficult to release because of the
adhesive forces: static electric, van der Waals and surface tension forces.
To understand the scaling effects and how they affect the micro world operation, it is important
to study the physics. The physics is well established for most aspects of our macro world, and
many work have been done in the difference field under different disciplines for the micro
world, such as in molecular biology, colloid science etc. In the following sections, we will
review some aspects of intermolecular forces and their effects in a larger scale - the micro
world. Intermolecular forces directly contribute to the forces we are interested. For example,
Coulomb forces contribute to the static electric forces; dipole interactions contribute to the van
der Waals forces and surface tension forces. Based on the understanding of those forces,
further details of the micro operation can be studied.

2. Intermolecular Forces
It is well know that there are four forces in nature: strong interaction, weak interaction,
electromagnetic interaction and gravitational interaction. The strong and weak interactions act
between neutrons, protons, electrons and other elementary particles, their range of actions is
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less than 10 nm . The electromagnetic and gravitational interactions act between atoms and
molecules as well as between elementary particles, their range of action is from subatomic to
practically infinite distance - from physics in daily life to inter galaxy interaction.
The forces we are most interested, in this contexts, are intermolecular forces which shape the
physics of micro world. Essentially, all intermolecular forces are electrostatic in origin. This is
indicated by the Hellman-Feynman theorem, which states that once the spatial distribution of
Notes on Microphysics

the electron clouds has been determined by solving the Schrdinger equation, the
intermolecular forces may be calculated on the basis of classical electrostatics. However, it is
rather difficult to solve the Schrdinger equation exactly, even for two the interactions of
hydrogen atoms in vacuum. Thus, it is useful to classify intermolecular interactions into
categories despite they come from the same origin:
Purely electrostatic in origin
such as interactions between charges, permanent dipoles and quadrupoles, etc.
Polarization forces arisen from the dipole moments
such as interactions in solvent medium etc.
Quantum mechanical in nature
such as covalent or chemical bonding; repulsive steric or exchange interactions, etc.
Other interactions
such as van der Waals force, magnetic force, etc.

2.1 The Effective Range of Intermolecular Forces

The effective range of intermolecular interactions are quite short, rarely exceeds 100 nm . The
reason of this is that the potentials and forces of intermolecular interactions decay very fast. If
we consider the total energy of one molecule with all the other molecules in its surrounding,
we have:
L

E(L) =

w ( r )4r dr
2

(1)

where is the diameter of the molecules, L is the size of the surrounding we consider and
w ( r ) is the interaction potential of two molecules having the general form:
C
w ( r ) = ----n
r

(2)

Thus, we get:
n3
4C

-1

E ( L ) = ---------------------------n3
L
( n 3 )

4C = ---------------------------n3
( n 3 )

for n > 3 and L

(3)

(4)

If n < 3 , the second term in (3) will be greater and the contribution from more distant
molecules will dominate over the nearby molecules, i.e., the size of the system must be taken
into account. The gravitational force has n = 1 and systems of inter galaxy distant could still
interact each other. Thus, the potentials of intermolecular forces do have n > 3 and this is the
reason that properties of material is generally not affected by its volume.

Notes on Microphysics

FIGURE 4. Common types of interactions between atoms, ions and molecules in vacuum.

Common types of interactions between atoms, ions and molecules in vacuum is listed in Fig. 4.
Their interactions energy decay generally according to the n > 3 rule except the charge-charge
interaction which will be discussed later.
Despite the short effective range of intermolecular forces, they determine the macroscopic
phenomena such as the height of rise of liquid in capillary channel, the breakup of water flow
into droplets, the shape of spiders web and the shapes of liquid droplets on surface (Fig. 5).
The reason underlying is that surface tension forces are the same as those that hold molecules
together in solids and liquids, and in both cases they arise from interactions acting over very
short distances.

FIGURE 5. Long range effects produced by short-range forces.

2.2 Intermolecular Interactions

Covalent Interaction
Covalent forces are forces that tightly bind the atoms together within the molecule. Their
effective range is about 0.1 0.2nm . The interatomic bonds formed by the covalent forces are
called covalent bonds. The covalent bonds are strong in strength which are in the range of
Notes on Microphysics

100 300 kT/bond (200 800 kJ/mol ). Depending on the position an atom or element
occupies in the periodic table, it can have a certain number of covalent bonds with other atoms.
The number is know as the atomic valency. Another property of covalent bonds is the
directionality - they are directed at specific angles relative to each other. The directionality of
covalent bonds determines the way the multi-valent atoms coordinates themselves in
molecules or in crystalline solids to from an ordered three-dimensional lattice.
Coulomb Forces
The Coulomb force, or charge-charge interaction, acts between two charged atoms (or ions).
Coulomb force is the strongest physical forces we are considering, which is stronger even than
most chemical binding forces. The free energy for Coulomb interaction between two charges
Q 1 and Q 2 is:
Q1 Q2
w ( r ) = ---------------4 0 r

(5)

where 0 = 8.854 10 C J m is the permittivity of free space, is the relative

permittivity or dielectric constant of the medium and r is the distance between the two
charges.
12

2 1

The Coulomb force is given by:

2

z1 z 2 e
Q 1 Q2
dw ( r )
-2 = -----------------F ( r ) = -------------- = -----------------2
dr
4 0 r
4 0 r
where e = 1.602 10

19

(6)

C is the elementary ionic charge, z 1 and z 2 are ionic valencies.

The electric field at a distance r away from a charge Q is defined by

Q
E ( r ) = -------------------2
4 0 r

Vm

(7)

Equation (5) indicates the potential of Coulomb interaction decay at speed of 1 r , which is the
same as gravitational force and has a very long effective range. This apparently break the rule
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stated in Section 2.1 - all intermolecular force laws must fall with distance faster than 1 r or
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1 r for energy. In reality, the positive ions are always surrounded by negative ions in lattice
or solution, which makes the electric field be screened and thus decays more rapidly away
from them than from an isolated ion. This results all Coulomb interactions between ionic
crystals, charged surfaces and dissolved ions much shorter range.
Polar Molecule Interactions
A electric dipole has two poles +q and q , and has net charge of zero. A molecular may have
a permanent dipole. Such a molecule is called polar molecule. The dipoles of some molecules
depend on their environment and can change substantially when they are transformed from one
medium to another. A dipolar ion is a dipole having different positive and negative charges.
The dipole moment of a polar molecule is defined as:

Notes on Microphysics

FIGURE 6. Ion-dipole interactions

u = ql

(8)

where l is the distance between the two charges +q and q .

As shown in Fig. 6, the energy of interaction between an ion and a polar molecule can be
computed by:
Qq
1
1
w ( r ) = -------------- ------- -------4 0 AB AC

(9)

let AB = r l cos 2 and AC = r + l cos 2 , we have

w ( r, ) = uE ( r ) cos

(10)

where E ( r ) is the electric field of the charge acting on the dipole:

Q
E ( r ) = -------------------2
4 0 r

(11)

Polarization of Molecules
Polarization means that the dipole moments induced in molecules by the electric fields
emanating from nearby molecules. The macroscopic dielectric constant of a medium is no
more than a reflection of the way the molecules of the medium are polarized by the local
electric field. Principally, all atoms and molecules are polarizable. Their polarizability is
defined according to the strength of the induced dipole moment uind acquired in a field E:
u ind = E

Notes on Microphysics

(12)

The Fig. 7 shows a one-electron atom with and without external field. When no external field
exist, u ind = 0 . When the atom is in a external field E the electrons orbit is shifted by a
distance l from the positive nucleus so that the induced dipole moments is u ind = 0 E = le ,
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where the polarizability of this case is 0 = 4 0 R .

FIGURE 7. Induced dipole in a one-electron atom.

Londons Forces or Dispersion Forces

The Londons forces or dispersion forces are caused by a momentary dipole moment between
atoms. The moment exist even for atoms which do not contain a permanent polarization.
Dispersion forces are quantum mechanical in origin and amenable to a host of theoretical
treatment of varying complexity. It may be understood intuitively as follows: for a non-polar
atom such as helium, the time average of its dipole moment is zero, yet at any instant there
exists a finite dipole moment given by the instantaneous positions of the electrons about the
nuclear protons. This instantaneous dipole generates an electric field that polarizes any nearby
neutral atom, including a dipole to an instantaneous attractive force between the two atoms, the
time average of this force is finite.

-e
l
+e

+e

l
-e

u=le

FIGURE 8. Two atoms affect each other.

The main features of dispersion force includes:

long range force, can be effective from large distances ( > 10nm ) down to interatomic
spacing (about 0.2nm )
may be repulsive or attractive, and in general does not follow a simple power law

Notes on Microphysics

 not only bring molecules together but also tend to mutually align or orient them, though this
orienting effect is usually weak
the dispersion interaction of two bodies is affected by the presence of other bodies nearby
(non-additivity of an interaction)
van der Waals Forces
van der Waals force originates from dipole-dipole interactions, it is contributed by three
important parts: Keeson-orientation, Debye-induction and the dispersion force. The energy of
all those three parts decays at the rate of 1 r 6 .
The Keeson interaction or orientation interaction is the angle averaged interaction between
two permanent dipoles, which has energy:
u 12 u 22
w ( r ) = -----------------------------------6
3 ( 4 0 ) 2 kTr
where 1kT = 4.114 10

14

for

u1 u2
kT > ----------------34 0

erg = 4.114 10

21

(13)

J at 298K(~25C ) .

The Debye interaction or induction interaction is the angle averaged interaction between
dipole and dipole-induce dipole, which has energy:
u2 0
w ( r ) = -------------------------( 4 0 ) 2 r 6

(14)

for two different molecules each possessing a permanent dipole moment u 1 and u 2 , and
polarizabilities 01 and 02 , the net dipole-induce dipole energy is:
u 12 02 + u 22 01
w ( r ) = --------------------------------( 4 0 ) 2 r 6

(15)

The Londons forces or dispersion forces contribute the third and probably the most important
part of van der Waals forces. They are always present. In the contrast, the other types of forces
may or may not present depending on the properties of the molecule. The interaction energy
between two identical atoms or molecules based on Londons equation is:
C disp
3 0 hv
3 0 I
- = --- ----------------------= --- ----------------------w ( r ) = -------------2
6
6
4 ( 4 ) r
4 ( 4 ) 2 r 6
r
0
0
2

(16)

where h = 6.626 10 J s is the Planck constant, v the orbiting frequency of the electron
and I = hv is the first ionization potential.
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for two dissimilar atoms:

hv 1 v 2
01 02
I1 I2
3 01 02 -------------------3--- ---------------------------------------=

w ( r ) = --- ----------------------2 ( 4 ) 2 r 6 ( v 1 + v 2 )
2 ( 4 ) 2 r 6 ( I 1 + I 2 )
0
0

(17)

Some properties of van der Waals forces:

Notes on Microphysics

 Non-additivity: unlike gravitational and Coulomb forces, van der Waals forces are not
generally pairwise additive - the force between any two molecules is affected by the
presence of other molecules nearby. This is because the field emanating from any one
molecule reaches a second molecule both directly and by reflection from other molecules
since they are also polarized by the field. This property normally reduce a small amount of
the total energy (less than 20%).
Retardation effects: when two atoms are distance apart, the time taken for the electric field
of the first atom to reach the second and return can become comparable with the period of
the fluctuating dipole itself. For example, the distance travelled by light during one rotation
of a Bohr atom electron is about 100nm . When this happens the field returns to find that the
direction of the instantaneous dipole of the first atom is now different from the original and
less favourably disposed to an attractive interaction. Thus, with increasing separation the
dispersion energy between two atoms begins to decay even faster then 1 r 6 and
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approaching a 1 r dependence at r > 100nm . This phenomenon is called retardation
effect. The retardation effects are more obvious in medium where the speed of light is
slower.

Notes on Microphysics