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Lecture 31
Chemical Bonding and Intermolecular forces- Part 2

Textbooks:
- Computational Materials Science: J. Gunn Lee
- Understanding Molecular Simulations: D. Frenkel and B. Smit
- Molecular Modelling Principles and Applications: Andrew Leach

- For this topic: Molecular Modelling Principles and Applications: Andrew Leach (chapter 4)

Prof. Divya Nayar, Department of Materials Science and Engineering

Recap
- Why intermolecular forces/chemical bonding are important to understand?
- Differences between chemical bonding and intermolecular forces
- The net force and net energy of interaction between atoms: attraction and repulsion

Pre-cap

- Different types of intermolecular forces

- Effect of these forces on properties of materials

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Difference between a chemical bond and intermolecular forces

• Electrons have dual nature: particle and wave
• The position of electrons can be described as the probability distribution (or electron cloud) that are
described by the wave functions.
• Any atom or molecule in isolation has a characteristic ground state electronic wavefunction and an
associated charge distribution

Chemical Bond Intermolecular Forces

• The electronic wavefunctions of the atoms • In many cases, when two atoms or molecules are

overlap to a significant extent and the brought together, no chemical bonds are formed but

electronic identity of the constituents is there is nevertheless attractive interactions. There is

appreciably modified on bond formation. no overlap of electronic wavefunctions of the atoms

• Binding energies of the order 100 kJ/mol. or molecules.
• Binding energies are of the order 10 kJ/mol.

Non-bonding Intermolecular forces

- Electrostatic interactions: originate from interactions between molecular multipoles. The strength
depends on 1/rn
e.g. Ion-ion, ion-dipole, dipole-dipole, dipole-quadrupole etc.

- Induction interactions: that arise from interaction between a static multipole moment of one
molecule and polarizability of the other molecule. Arise from distortion in charge distribution.
E.g. ion-induced dipole, dipole-induced dipole

- London or dipersion forces: originates from correlations between instantaneous dipoles of

neighboring atoms. Arise from fluctuations in charge distribution.

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Multipole: A set of partial charges arranged in a symmetric manner

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“Non-bonding” Intermolecular forces

Bond Attraction Energy Example Model
(kJ/mol)

Ion-dipole Ion-dipole 40-600 Na+ ---- H-Cl

Dipole-dipole Dipole-dipole 5-25 H-Cl---- H-Cl

ion-induced dipole ion-polarizable 3-15 Na+ ---- H-H

electron cloud

Dipole-induced Dipole- 2-10 H-Cl---Cl-Cl

dipole polarizable
electron cloud

London dispersion Polarizable 0.05-40 Cl-Cl---Cl-Cl

forces electron cloud

General functional form of the van der Waals energy

𝜎 !" 𝜎 #
𝑈 𝑟 = 4𝜖 −
𝑟 𝑟
Lennard-Jones Potential

- Weak interactions
- Ubiquitous in nature
- Non-directional bonding

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Hydrogen bonding
- It is intermediate between electrostatic interactions and a true chemical bond
- The energy of interaction lies between that of a covalent and an ionic bond (20-30 kJ/mol).
- Formed between a H covalently bonded to an electronegative atom (donor) and an electronegative
atom (acceptor)
- Interaction of a bonded pair with a lone pair of electrons.
- Directional bonding

Hydrophobic interactions
- Interactions between non-polar solutes (hydrophobes) in water.
- Water molecules reorganize around the hydrophobe in an
ordered manner that is entropically favourable at low
temperatures.
- At high temperatures, the ordering of water is broken and
enthalpically it is favourable to solvate the hydrophobe. Methane clathrates Oil in water
- Often found in biomaterials.
Hydrophobic solvation
Hydrophobic association
(a) Hydrophobic Solute (b) Hydrophobic (c) Hydrophobic
Not Yet Mixed Solute Solute 16 Surface Units + 16 Surface Units
with Water in Cold Water in Hot Water Figure 31.8 Why do nonpolar solutes
associate in water? Association reduces
the total surface area of contact +
(a) Partial Molar
between solute molecules and the
Volume of Solvation
surrounding water. When the two
v (cm3 mol−1) solutes are separated, they have, in
total, 32 units of surface contact with
300
the solvent. But when the solutes
contact each other, they have only 24
200 units of surface contact with water.

100 24 Surface Units

0 Surface areas
400 500 600Table 31.2
Figure 31.3 The ‘iceberg’ model of the heat capacity of (a) the transfer of nonpolar A of small nonpolar solutes,
and numbers Nw Constrict
Alcohols the Volumes
T (K)
solutes into water [3, 4]. (This picture is only a two-dimensional cartoon, showing of first-
Molecular Driving
fewer first-shell forces:
waters thanDill
in and Bromberg
real three-dimensional water.) (b) In cold water (near in waters.
neighbor Mixtures with Water
(b) Enthalpy of Solvation
room temperature), the water molecules surrounding the nonpolar solute form good
hydrogen bonds (low energy), in structured cages (low entropy) that ∆h◦avoid
(kJ mol−1)
‘wasting’ Solutes at high concentrations can disrupt the structure of water. Figure 31.10
A (Å2 )
10 hydrogen bonds. (c) In hot water, more first-shell water conformations are accessible
150 bonds and/or
Molecule Nw
shows the partial molar volumes of alcohols in mixtures of alcohol and water,
(higher entropy), but some of them have weaker or unformed hydrogen CH4 as a function
152.36of alcohol
17 concentration. Adding a small amount of alcohol to
van der Waals interactions (higher energy). This contributes to the100 heat capacity C2 H6 water leads to a constriction.
191.52 21 The volume of the mixture is smaller than the
because the system enthalpy increases with temperature.
C3 H8 sum of 223.35
volumes of25 the pure alcohol and pure water components. The water
50
N2 molecules pack better
142.41 16 around the alcohol molecules than around other water
corresponding to a free energy of about 6.1 kcal mol−1 at T =0300 K opposing CO molecules. However,
145.31 16at higher concentrations, alcohol molecules pervade the
dissolution of oil in water. O2 system 135.74
so extensively
15 that they disrupt the fluctuating network of hydrogen-
200molecule
400 is a 600
Figure 31.4 shows why the restriction factor of 1/2 per water
reasonable estimate [5, 6]. Figure 31.4(a) shows a water molecule at the center T (K)
Ne
He bonded105.68
water polygons.
116.13 13
12
5
of a tetrahedron. The figure shows the six different ways the central water can
Figure 31.7 (a) The partialAr 143.56
Ions Can Make 16
or Break Water Structure
point its two hydrogen-bonding arms toward the vertices of the tetrahedron,
molar volume v and (b) the Kr 155.70 17
hydrogen bonding to neighboring waters in bulk water. Now,enthalpy
suppose ∆hthe
◦
of back
solvation ofXe 168.33 19
neonmolecule.
gray dot water molecule in Figure 31.4(a) is replaced by a solute in water diverge
How as the Kosmotropic and Chaotropic Ions
temperature approaches Source:Cause Water
SJ Gill, SF Ordering
Dec, or Disordering
many ways can the central water now orient if it must avoid pointing either theG Oloffson, and I Wadsö,
critical temperature of
of its hydrogen-bonding arms towards the solute vertex? Figure 31.4(b) shows J Phys Chem 89, 3758–3761
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Superhydrophobic surface

In nature

Appl. Phys. A 125, 261 (2019) doi:10.1016/j.crme.2011.11.002

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Bonding character and properties

_c12_414-459 12/6/05 20:13 Page 427
REVISED PAGES
- Melting and boiling temperatures: covalent and ionic solids have higher melting and
boiling points.
- When a solid consists of molecules held together by secondary bonds, the melting and
boiling points of the solid reflect only the strength of the secondary bonds between the
molecules, and not the strength of the primary 12.3 Silicate Ceramics • 427
bonds within the molecule.
Figure 12.10 The arrangement of silicon and oxygen
atoms in a unit cell of cristobalite, a polymorph of SiO2.

Si4+ O2–

- 3-D network of Si-O bonds - Secondary bonding: van der Waals forces between CH4 molecules
- No secondary bonding (strength 1.36 kJ/mol)
If these
- Melting pointtetrahedra
of 1723 ℃ - ordered
are arrayed in a regular and Melting manner,
point of a-182 ℃
crystalline
- structure is formed.
During melting Si-OThere
bonds are
arethree - C-H bond
primary polymorphic
broken strength
crystalline formsis 413 kJ/mol > Si-O strength of 375 kJ/mol
of sil-
- Their
ica: quartz, cristobalite (Figure 12.10), and tridymite. During melting are
structures vanrelatively
der Waals forces are weakened
complicated, and comparatively open; that is, the atoms are not closely packed to-
gether. As a consequence, these crystalline silicas have relatively low densities; for
12 example, at room temperature quartz has a density of only 2.65 g/cm3. The strength
of the Si–O interatomic bonds is reflected in a relatively high melting temperature,
1710#C (3110#F).

Silica Glasses
Silica can also be made to exist as a noncrystalline solid or glass, having a high de- 6
gree of atomic randomness, which is characteristic of the liquid; such a material is
called fused silica, or vitreous silica. As with crystalline silica, the SiO4"
4 tetrahedron
is the basic unit; beyond this structure, considerable disorder exists. The structures
for crystalline and noncrystalline silica are compared schematically in Figure 3.22.
Other oxides (e.g., B2O3 and GeO2) may also form glassy structures (and polyhe-
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- Thermal expansion: asymmetry of the potential energy versus distance curve

- Thermal expansion at a given temperature tends to be less for strongly bonded materials than for
weakly bonded materials.
- Deep potential wells are more symmetrical about the equilibrium position r0 than shallow
potential wells.

- Mechanical Properties of solids are dependent on the strength of the bonds as well as the
directional nature of bonding.
- Solids with strong and directional bonds tend to be brittle
- Diamond: covalently bondedà hard and brittle
- Metallic bonds are relatively weak and nondirectional, metals are soft, ductile and malleable.
- Ionic solids fall in between covalent and metallic solids in that they may exhibit a very limited
amount of ductility.

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Why do we need to understand the intermolecular forces?

Designing superhydrophobic Designing materials stronger than Kevlar Designing materials with adhesive properties
surfaces, self-cleaning
applications SEM image of spider silk fiber SEM image of Gecko feet

Hydrophobic interactions Hydrogen bonding Van der Waals forces

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Computational Materials Science

Modeling and Simulations: Not just an extra tool!

• Can act as a bridge between theory and experiments

• Can help in validating a theory

• Can help in understanding problems under extreme conditions where

experiments are not feasible

• Can provide additional insights into experiments

• Can help in designing and predicting new materials: motivating new

experiments

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Three pillars of science

Simulations (or
Computation)
Experiment

Theory

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The ingredients
Computer, Programming, Models, Simulation…

Ada Lovelace
(1815-1852)
Analytical Engine: First computer
Ada Lovelace broke gender barriers
like never before and went on to
discover computer progamming
175 years ago, an industry still
dominated by men.

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Computational Materials Science

F = ma

Theory

High Performance
Computing

Modeling and simulations Computational microscope !

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A computational
Basic recipe.. experiment
The Recipe

• Define the
whatproblem

to calculate.

• Make a MODEL (that represents the real system properly)

• Select the relevant rules (THEORY)

• Write a code or use a software to do the job

• Run the SIMULATION

• Analyze the data produced

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Dream Decipher, Design, Discover… Develop

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