Prof. Dr.

Ulrich Jonas

Fundamental Interactions: 6 Forces Macromolecular Chemistry

Department Chemistry - Biology
University of Siegen

In nuclear and high-energy physics 6 fundamental forces are recognized, which describe the
structure of matter.

- the strong interaction act inside the nucleus, range < 10-5 nm
- the weak interaction ~ 1/10000 of the diameter of an atom

source of all intermolecular forces !

- the electromagnetic interaction
(Hellman-Feynman)

- gravitation very long-range between macroscopic objects,

negligible between molecules

- the super-strong interaction very particular forces only used in nuclear

- the super-weak interaction physics (don't bother...)

Hellman-Feynman theorem: "Once the spatial distribution of the electron clouds has been
determined by solving the Schrödinger equation, the intermolecular forces may be calculated
on the basis of straightforward classical electrostatics."
 Feynman diagrams
Fundamental Interactions: Details
neuton (n) p
- the strong interaction: nuclear interaction (holds protons & neutrons in the nucleus
together by exchange of pions), very fast (about the time a photon c travels through a pion
time
proton ~ 10-23 s), acts between "hadron" (nucleons, mesons, hyperons), not between
"leptons" (electrons, myons, neutrinos) at a distance of < 10-15 m

positron proton (p) x n

n
(e+)
- the weak interaction: nuclear interaction (responsible for nuclear -decay / electron
W emission & and slow decay of elementary particles), time scale varies considerably (10-10 -
103 s), interaction involves "leptons", depends on the parity (symmetry of translation &
spin) of the particles, acts over distances << 10-15 m (below strong interaction)
(W: hypothetical particle mediating weak force)
p antineutrino p e
photon
- the electromagnetic interaction: binds electrons to nucleus, binds atoms to molecules,
responsible for all chemistry and biology, acts in electron-positron annihilation, time scale lies
between strong and weak interaction, interaction is mediated by the photon, acts primarily
between charged particles over infinite distance (in principle), is neutralized by opposite charge
p e

- gravitation: longest known & least understood, negligible in molecular dimensions, but important for
mesoscopic to macroscopic objects (like in buoyancy or droplet deformation), acts attractive between all
matter, very long range (between galaxies, e.g.) w(r) = -G m1 m2 / r G = 6.67 x 10-11 N m2 kg-2

relative interaction strength: strong (15) : el.mag. (1/137) : weak (10-12) : gravitation (10-35)
 Pair Potentials
- van der Waals: deviation of behavior of real gases from ideal gas law (pV = nRT):
a
p 2
V b RT
V

{
excluded volume of atoms / molecules

{
attractive intermolecular forces ( van der Waals forces)

A B
- Mie: general interaction "pair potential" to describe w r
rn rm

{
{
complex intermolecular interactions:
repulsive term
attractive term
- Lennard-Jones:

A B
w r
r6 r 12
w/F

{
{ very short-range "hard sphere"
repulsion
long-range attractive van der Waals
r
interaction
Long / Short-Range Forces and Strong / Weak Forces

The interaction parameter X determines the strength of the interaction.

the larger X the stronger the interaction

X
strong w weak
rn

long-range
X short-range
w
rn

The exponent in the distance variable r determines the range of the interaction.
the larger the exponent n the shorter the interaction range
 Types of Interactions: Overview 1

type of interaction interaction energy w(r)

J. Israelachvili; "Intermolecular and Surface Forces", Second Ed.; Academic Press Limited: London, 1995, p. 28
 Types of Interactions: Overview 2

type of interaction interaction energy w(r)

J. Israelachvili; "Intermolecular and Surface Forces", Second Ed.; Academic Press Limited: London, 1995, p. 28
 Intermolecular Interactions:

red. HS
• covalent: S S
e.g. disulfide bonds ox. SH

• ionic:
NH3 mica
e.g. ammonium salts on mica

• H-bonding:
e.g. DNA double helix
NH3
• coordinative:
e.g. transition metal complexes Co

• dipole-dipole:
e.g. nitroaniline in zeolite H2 N NO2 H2N NO2

µ µ

• dispersion:
e.g. alkyl chains

• charge transfer (CT): e.g. intercalation of trinitrofluorenone

into triphenylene columns

• topological link: • catenanes / rotaxanes

• endohedral fullerene complexes
• form anisotropy: • liquid crystals
• ordered colloidal dispersions
 Chemical Bonds: Covalent, Ionic, Metallic, Coordinative
Chemical bonds: strong bonds between atoms to form molecules and extended solids.
relates to cohesion within a covalent bonded material
R R
R
Examples in surface sciences:
H H H H

-covalent surface bonds: hydrosilylation of hydrogen Si Si Si Si Si Si

terminated silicon surface (radical, thermal, photochem., R R R

catalytic):

N N N
-ionic surface bonds: quaternary ammonium salts on mica:
mica

-metallic surface bonds: interface between two metal layers:

-coordinative surface bonds: CO adsorbates on d-transition

metal surfaces (somewhere between covalent and
coordinative):
 Covalent Bond
Sharing of valence electrons (in pairs) between two atoms (usually non-metals) leads to a
covalent bond between these atoms molecules

single bond: H H H H H H two s-orbitals overlap to form a -bond

H H H H two sp2-orbitals overlap to form a -bond

double bond: C C
H H two p-orbitals overlap to form a -bond
H H
two sp-orbitals overlap to form a -bond
triple bond: H C C H H H four p-orbitals overlap to form two -bonds

bond length (pm) energy (kJ mol-1)

type
C-C 154 347-356
C=C 134 611-632
C C 120 833-837

equal distribution of bonding electrons between atoms leads to non-polar bond (H-H)
localization of bonding electron pair towards one atom (more electronegative) leads to polar
bond (H +-Cl -) extreme case: ionic bond
 Covalent Bond: VB and MO theory
VB theory: In the valence bond (VB) theory resonance energy is gained by exchange of
electrons between two atoms (orbital overlap). Bonding electrons are localized between two
bonding atoms and are not distinguishable.
description of bonding geometries by hybrid orbitals:
four C valence electron orbitals: four C sp3 hybrid orbitals (tetrahedral):
2s 2px 2py 2pz sp3
(e.g. CH4)

MO theory: In the molecular orbital (MO) theory bonding electrons are not localized between
two atoms of a bond, but distributed in a group of molecular orbitals over the entire molecule.
quantum mechanical description by the Schrödinger equation: H MO
=E MO

MO are generated by a linear combination of atomic orbitals (LCAO):

MO
= c1 + c2 + c3 + ... + cn n
wave function of MO: MO
; atomic orbital (AO): n
antibonding
(H·) 1s 1s (H·) MO theory is basis for computational treatment of
molecular structure (semi-empirical, ab-initio)
bonding
frontier orbitals HOMO / LUMO
(H-H)
 Ionic Bond

ionic bonds are formed by strong Coulomb interactions between two oppositely charged
species (e.g. Na+Cl-)

the potential energy varies with the distance r between the two ions by 1/r (the force
varies with 1/r2)

description by formal electron transfer from newly formed cation (usually metals) to newly
formed anion (usually non-metals)

"simplest bond" / extreme case of polar bond

ionic bond is not localized / directed, but acts isotropically / radial-symmetrically around
ions leads to extended aggregation and ionic crystals with one cation being
surrounded by many anions and vice versa
- - +

+ - - + - - + - + etc.

3D
- - +
 Metallic Bond

metallic bond: attractive interactions / bonds in metals are mediated by free moving valence
electrons (electron sea) between positively charged atoms over entire sample

- electron sea: high electron mobility good thermal and electrical conductivity

- metallic bond is weak (compared to covalent bond) ductile metals

theoretical description of metallic bond by band theory:

 Electrostatic Interactions
The force F (Coulomb force) acting between two charges q1 and q2 separated by a distance r in
vacuum ( 0) depends on the separation by 1/r2.
F/V
q1 q 2 q1 q2
q1
r
q2
F 2 in medium F 2 V=1/r
4 0r with r 4 0 r r
F=1/r2
(relative permittivity, dielectric constant)
r

the electrostatic forces are additive: in a system of many charges the force on a single
charge is obtained by summing all the interactions with the other charges
r
- electrical work we:
q1 q 2
w e or V F dr
potential energy V: 4 0 r r
q2
- electric potential: we or V = q1
4 0 r r
q2
- electric field strength: E 2
F = q1 E
4 0 r r
 van der Waals Interactions

Collection of attractive interactions between molecules based on dipole / dipole, dipole /

induced-dipole, and induced-dipole / induced-dipole interaction (Keesom, Debye, London
dispersion energies)

dipole moment : equal charge q separated at a fixed distance r

=qr -q +q unit: debye (D) = 3.336 10-30 C m

r

induced dipole i
: dipole induced in a polarizable molecule by electric field

- +
: polarizability
i
= E E : electric field

E
 Dipole / Dipole Interactions

Interaction of freely rotating dipoles (liquid) depends on the thermal energy (kT) and is
referred to as Keesom energy (Boltzmann distribution of orientations).

preferred over

2 1 2 1
V
3 kT 4 0 r6

At 25°C the average interaction energy for pairs of molecules with µ = 1 D is about -1.4 kJ mol-1
when the separation is 0.3 nm.
The average molar kinetic energy at 25°C is 3/2 RT = 3.7 kJ mol-1.
 Dipole / Induced-Dipole Interactions

A dipole near a polarizable molecule induces a dipole (charge dislocation) in the neutral
molecule leading to an attractive interaction, the corresponding potential energy is referred
to as Debye energy.

+
-
equal to +
-
'
µ
2
' 1
V 6
4 0 r

' is the polarizability volume given by '= /4 0

(unit: cm3)

The interaction energy is independent of the temperature because the induced dipole follows
immediately the motion of the permanent dipole and is thus not affected by thermal motion, and
it depends on 1/r6 (like the dipole / dipole interaction).
For a molecule with µ = 1 D (e.g. HCl) near a molecule with polarizability volume ' = 10-23 cm3
(e.g. benzene) the average interaction energy is about -0.8 kJ mol-1 at a separation of 0.3 nm.
 Induced-Dipole / Induced-Dipole Interactions

Random fluctuations in a polarizable molecule lead to a temporary dipole which induces a

corresponding dipole in a nearby molecule, leading to attractive dispersion interactions.
The involved potential energy is called the London dispersion energy.

parallel orientation anti-parallel orientation

+
-

+
+
-

-
+
'

3 1 2 1 I1 I 2 3 1 ' ' I1 I 2
2
V 2
2 4 0 r 6 I1 I 2 2 r 6 I1 I 2
In is the ionization energy, with I = h , is the electronic absorption frequency

In the case of two methane molecules with ' = 2.6 · 10-24 cm3 and I = 7 eV the dispersion
energy becomes -5 kJ mol-1 for a separation of 0.3 nm (comparable to the enthalpy of
vaporization of methane Hvapor = 8.2 kJ mol-1).
 van der Waals Forces Between Macroscopic Objects

The van der Waals forces between two macroscopic bodies can be calculated (as
approximation) by integrating over the molecular / atom-atom vdW pair potential ( w(r) = -C / r6)
of all molecules / atoms in one body with all molecules / atoms in the other body.

interaction free energies are expressed in terms of the Hamaker constant:

A= 2C 1 ~ 10-19 J (in vacuum)
with 1/2 being the atom density of body 1 / 2, C is the coefficient in the molecular / atom-
atom pair potential

D
 Hydrogen Bonding
highly polarized bond of hydrogen with heteroatom (e.g. -X --H +, X = O, N, F) provides
strong protonic character to hydrogen (proton donor) H can interact with electron
donating group / atom / electron lone pair (proton acceptor) H-mediated "bond"

elongation of bond in H-donor

very short distance of H and electron donor

(H-acceptor)

for H2O: O-H = 0.10 nm, O...H = 0.176 nm,

theoretical vdW radius O/H = 0.26 nm

H-bonding in H2O:
particular structure of ice

hydrophobic effect (restructuring of H-bonding

network around hydrophobic solute is
entropically unfavorable)
 Hydrogen Bonding: Proteins

Hydrogen bonding of the amide groups via N-H...O=C leads to

secondary and tertiary structures of proteins:
- -helix (chiral, tubular structure)
- -pleated sheet (extended flat structure)

a-helix
-pleated sheet
 Hydrogen Bonding: DNA
The base pairing in the DNA double helix is mediated by hydrogen bonding between the
nucleic acid moieties:
- 2 H-bonds between adenine and thymine
- 3 H-bonds between guanine and cytosine