Weak Interactions

Non-Covalent Interactions

MATERIALS SCIENCE
Part of & AALearner’s Guide
Learner’s Guide
ENGINEERING
AN INTRODUCTORY E-BOOK
Anandh Subramaniam & Kantesh Balani
Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
http://home.iitk.ac.in/~anandh/E-book.htm
Weak Interactions
 We will discuss here about intermolecular weak interactions
 The strong ‘bonds’ are: Covalent, Ionic and Metallic
 How do we get a measure of non-covalent interactions?

 Boiling point (being the temperature at which vapor pressure of substance equals the
ambient pressure) is a better measure of non-covalent forces as compared to Melting point
(which not only influenced by Attractive forces but also the crystal packing)

Boiling point Electronegativity

difference

NaCl → 1413 C
O
Decreasing BP

H2O → 100C EN = 3.5O  2.1H = 1.4

H+ H+
Polar covalent

BrF → 20C EN = 4.0F  2.8Br = 1.2

Br+ F
Polar covalent

Ar → 186C Ar
1.91

Schematics
 Bonding

Inter-molecular Intra-molecular
Hydrogen bond COVALENT

Van der Waals , , …

Dipole-dipole

Dipole- Induced dipole

Instantaneous dipole-induced dipole London Dispersion

Ion-dipole
Etc.
Cation-Pi
Relative strengths
Pi-Pi dispersion forces < dipole-dipole interactions < hydrogen bonds

The term ‘Van der Waals forces’ is sometimes used for a specific type (London Dispersion) rather than the class
We will describe briefly a few of these (only) here

rther reading
Noncovalent Interactions: A Challenge for Experiment and Theory, Klaus Müller-Dethlefs and Pavel Hobza, Chem. Rev. 2000, 100, 143−167
 Hydrogen bond

 The covalent boding between a hydrogen atom and a strongly electronegative atom becomes ‘polar’-
covalent
 The ‘charged’ hydrogen ‘ion’ can be attracted to a electronegative atom, such as nitrogen, oxygen or
fluorine
 hydrogen bond should not be confused with a covalent bond to hydrogen.
 Types of hydrogen bonds:
 Intermolecular (between molecular)
 Intramolecular (within a molecule)
 E.g. of hydrogen bonding: water (responsible for the high boiling point of water compared to say H 2S),
DNA, partly responsible for the secondary, tertiary, and quaternary structures of proteins and nucleic
acids, Polymers

Hydrogen bond O

H+ H+
O

H+ H+

Schematics
Ice crystallizes in many polymorphic forms (12 crystal structures and 2 amorphous forms known)- we consider one form here

Hydrogen bonded Ice crystal (hexagonal)

[0001]

 Packing fraction → ~0.34

 Note the low packing fraction in spite of having the same space group as HCP crystals
 c/a ratio → 1.628 (very near ideal ratio of 1.633)

Value
Lattice parameter(s) a = 4.52 Å c = 7.37 Å
Space Group p63/mmc
 Van der Waals

Dipole- Dipole interactions

 In the covalent bonding between two atoms of very different electronegativity the bond becomes
highly polar (introducing partial charges on the species)
 This dipole can interact with other permanent dipoles
 This interaction is stronger than dispersion forces

Diplole-Dipole Interaction

Br+ F Br+ F

Schematics
 Instantaneous dipole-induced dipole London Dispersion

 Instantaneously generated dipole (due to asymmetry in electron charge distribution around the
nucleus) on one atom leads to slight polarization of the atom
(→ quantum induced instantaneous polarization)
 This induces a dipole on the neighbouring atom (temporarily)
 The force between these two dipoles is called the London dispersion forces
 The force is very weak and is temporally varying
 Can operate between non-polar molecules (H2, Cl2, CO2 etc.)
 The strength of the dispersion forces will increase with number of electrons in the molecule

Ar Ar
+ 

Schematics
 Ion-Dipole

 Permanent dipole interacts with an ion.

 This explains for example the solubility of NaCl in water.
 The figure below shows the interaction of Na + and Cl ions interacting with the permanent dipoles in a
water molecule.

Schematics