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Solid State Physics

Bonding in Crystals
Dr. rer. nat. Muldarisnur

JURUSAN FISIKA UNIVERSITAS ANDALAS


Interatomic Binding
 All of the mechanisms which cause bonding between atoms comes from
electrostatic interaction between nuclei and electrons.

 The strengths and types of bond are determined by the particular


electronic structures of the atoms involved.

 The existence of a stable bonding arrangement implies that the spatial


configuration of positive ion cores and outer electrons has less total
energy than any other.

 The energy deficience of the configuration compared with isolated atoms


is known as cohesive energy, and ranges in value from 0.1 eV/atom for
solids

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Energies of Interactions Between Atoms
 The energy of the crystal is lower than that of the free atoms by an
amount equal to the energy required to pull the crystal apart into a
set of free atoms. This is called the binding (cohesive) energy of the
crystal.

• NaCl is more stable than a collection of free Na and Cl.


• Ge crystal is more stable than a collection of free Ge.

Cl Na NaCl

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Why do atoms form bonds?
 Bonds involve the electrons in the outer shells of atoms.
 Each shell has a maximum number of electrons that it can hold.
Electrons fill the shells nearest the nucleus first (Aufbau Principle).

1st shell holds a maximum of 2


electrons

2nd shell holds a maximum of 8


electrons

3rd shell holds a maximum of


18 electrons

Filled-electron shells are very stable.


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Valence Electrons
8A
1A

2A 3A 4A 5A 6A 7A

Number of valence electrons is equal to the Group


number.
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Why do atoms form bonds?
 The atoms of noble gases have completely full
outer shells and so are stable.

 This makes the noble gases very unreactive and


so they do not usually form bonds.

 The atoms of other elements have


incomplete outer electron shells
and so are unstable.

 By forming bonds, the atoms of these


elements are able to have filled outer
shells and become stable.

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Energies of Interactions
• This typical curve has a
minimum at equilibrium V(R)
distance R0
• R > R0 ;
• the potential increases Repulsive
gradually, approaching 0 as
R∞
0
• the force is attractive R0 R
• R < R 0; Attractive
• the potential increases very
rapidly, approaching ∞ at R
r
small separation.
• the force is repulsive

Force between the atoms is the negative of the slope of this curve. At
equlibrium, repulsive force becomes equals to the attractive part.
Solid State Physics Dr. rer. nat. Muldarisnur 7
The potential energy of interatomic interaction
repulsive
V(r) Repulsive force a Pauli exclusion principle prevent
the crystal from collapsing
Attractive force a bonding hold atoms together to
form solid
equilibrium distance
r
Distance between
two atoms
Types of bonding:
attractive 1. Ionic bonds
2. Covalent bonds
V (r ) 3. Metallic bonds
Interatomic force F (r )  
r
4. Van der Waals
V
equilibrium distance 0 5. Hydrogen
r r r0

Solid State Physics Dr. rer. nat. Muldarisnur 8


Energies of Interactions
The potential energy of either atom will be given by:

V= decrease in potential energy+increase in potential energy


(due to attraction) (due to repulsion)

a b
or simply: V (r )  m  n
r r

V(r): the net potential energy of interaction as function of r

r: the distance between atoms, ions, or molecules

a,b: proportionality constant of attraction and repulsion, respectively

m, n: constant characteristics of each type of bond and type of structure

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Lennard-Jones Potential
 Attraction due to instantaneous dipole of molecules
 Short range force
 Use cut-off radius to reduce computations  &  are empirical
parameters chosen by fits to data.
300

250

200
Argon gas
     
12 6 150

 4      
v(r)/kb (K)
100
U LJ
 r   r   50

0
0.3 0.5 0.7 0.9 1.1 1.3 1.5
-50

-100

-150
r (nm )

Solid State Physics Dr. rer. nat. Muldarisnur 10


Lennard Jones potentials
 The Lennard-Jones potential

 
 
12
  

6

u r   4       
LJ

 r   r  

 The truncated Lennard-Jones potential


u LJ r  r  rc
u r   
 0 r  rc
 The truncated and shifted Lennard-Jones potential
u LJ r   u LJ rc  r  rc
u r   
 0 r  rc
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Lennard-Jones Potential: Noble Gas Atoms

Solid State Physics Dr. rer. nat. Muldarisnur 12


Lennard Jones potentials
Some Lennard-Jones potential examples of application are listed in
the Table. Even this crude interaction model has extensive
applications. This model can explain many properties of gases, solids
and liquids quite well.
Minimum interaction energy and its distance
r0(A) (J)

He 2.2 110 -22

H2 2.7 4

Ar 3.2 15

N2 3.7 13

CO2 4.5 40

Solid State Physics Dr. rer. nat. Muldarisnur 13


Example – Lennard-Jones (LJ) clusters
21/6σ
   12    6  E
E  4       
 R   R  
Two atoms:  
R R

ε
repulsion dispersion (van der Waals)
Multiple atoms -    12    6 
a E  4       
assume pairwise  
i  j  R ij 
R  
1 2 3   ij  
additive:

b Isomers
1 3 2 • different minima on potential energy surface
• number of isomers grows exponentially
with # of atoms
c • a and b – permutation-inversion isomers
• Ea = Eb ≠ Ec
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Chemical Bond
 Types of Chemical Bond: Ionic and Covalent
 Inoinzation energy: the energy required to remove an electron from a
neutral isolated atom to form an ion with one positive charge
 Electron affinity: the amount of energy released when an electron is
added to a neutral isolated atom to form an ion with one negative
charge.
 Electronegativity: the average of the first ionization energy and the
electron affinity. It is the measure of the ability of an atom or molecule to
attract electrons in the context of a chemical bond.
 Chemical bonding between two atoms is determined by the difference in
electronegativity
Large difference a ionic bonding
e.g. Na-Cl (3.16 - 0.93 = 2.23)
Small difference a covalent bonding
e.g. C-O (3.44 – 2.55 = 0.89)
O-O (0)
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Electronegativity vs Bond Type

Solid State Physics Dr. rer. nat. Muldarisnur 16


Atomic Bonding
 Atoms in solids are hold by interatomic forces

 The binding energy of the atoms in all solids results from the reduction in
energy of atomic electrons due to the proximity of the neighboring atoms

Primary Atomic Bonding Secondary Atomic Bonding

Ionic Covalent Metal Van Der Waals Hydrogen

Dipole - dipole
Polar Non Polar
Dipole – non dipole

Dispersive Force (London)

Solid State Physics Dr. rer. nat. Muldarisnur 17


Classification of Solids by Atom Type & Type of Bonding

This chart continues on the next!


Solid State Physics Dr. rer. nat. Muldarisnur 18
Classification of Solids by Atom Type & Type of Bonding
The chart on the previous page :

MP: Melting point BP: Boiling point


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Types of Primary Bonds

Ionic : Electrostatic
attraction between ions.

Covalent : Sharing of
electrons.

Metallic : Metal atoms


bonded to several other
atoms.

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Ionic Bonds
 Metal - nonmetal.
 Metal loses electrons to form cation, while nonmetal gains electrons
to form anion.
 The electronegativity between the metal and the nonmetal must be
larger than 2.
 Ionic bond results from + to − attraction.
 Larger charge = stronger attraction.
 Smaller ion = stronger attraction.

 Ionic bonding is due to the electrostatic force of attraction between


positively and negatively charged ions (between 1A and 7A).

 All ionic compounds are crystalline solids at room temperature


Solid State Physics Dr. rer. nat. Muldarisnur 21
Ionic Bonds
 The metallic elements have only up to the valence electrons in
their outer shell will lose their electrons and become positive
ions.
 Whereas, electronegative elements tend to acquire additional
electrons to complete their octed and become negative ions, or
anions.

Na Cl

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Ionic Bond
Ionic bonds are formed by the attraction of oppositely charged ions.

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Properties of Ionic Compounds
 Crystalline structure.
 A regular repeating arrangement of ions in the solid.
 Ions are strongly bonded.
 Structure is rigid.
 High melting points- because of strong forces between
ions.

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Ionic Bonding
The equations that we will use to predict lattice energies for crystalline solids are the
Born-Mayer equation and the Kapustinskii equation, which are very similar to one
another. These equations are simple models that calculate the attraction and
repulsion for a given arrangement of ions.
Born-Mayer Equation:
U0 = (e2 / 4  0) * (N zA zB / d0) * A * (1 – (d* / d0))
U0 = 1390 (zA zB / d0) * A * (1 – (d* / d0)) in kJ/mol

Kapustinskii equation :
U0 = (1210 kJ Å / mol) * (n zA zB / d0) * (1 – (d* / d0))

Where:
e is the charge of the electron, 0 is the permittivity of a vacuum
N is Avogadro’s number
zA is the charge on ion “A”, zB is the charge on ion “B”
d0 is the distance between the cations and anions (in Å) = r+ + r-
A is a Madelung constant
d* = exponential scaling factor for the repulsive term = 0.345 Å
n = the number of ions in the formula unit
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Ionic Bonding
The origin of the equations for lattice energies. U0 = Ecoul + Erep
The lattice energy U0 is composed of both coulombic (electrostatic) energies and an additional
close-range repulsion term - there is some repulsion even between cations and anions because
of the electrons on these ions. Let us first consider the coulombic energy term:

For an Infinite Chain of Alternating Cations and Anions:

In this case the energy of coulombic forces (electrostatic attraction and repulsion) are:
Ecoul = (e2 / 4  0) * (zA zB / d) * [+2(1/1) - 2(1/2) + 2(1/3) - 2(1/4) + ....]
because for any given ion, the two adjacent ions are each a distance of d away, the
next two ions are 2d, then 3d, then 4d etc. The series in the square brackets can
be summarized to give the expression:
Ecoul = (e2 / 4  0) * (zA zB / d) * (2 ln 2)

where (2 ln 2) is a geometric factor that is adequate for describing the 1-D nature of
the infinite alternating chain of cations and anions.
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Ionic Bonding
For a 3-dimensional arrangement, the geometric factor will be different for each
different arrangement of ions. For example, in a NaCl-type structure:

Ecoul = (e2 / 4  0) * (zA zB / d) * [6(1/1) - 12(1/2) + 8(1/3) - 6(1/4) + 24(1/5) ....]

The geometric factor in the square brackets only works for the NaCl-type structure,
but people have calculated these series for a large number of different types of
structures and the value of the series for a given structural type is given by the
Madelung constant, A.
This means that the general equation of coulombic energy for any 3-D ionic solids is:
Ecoul = (e2 / 4  0) * (zA zB / d) * A
Note that the value of Ecoul must be negative for a stable crystal lattice.
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Ionic Bonding
The numerical values of Madelung constants for a variety of different structures are
listed in the following table. CN is the coordination number (cation, anion) and n is
the total number of ions in the empirical formula e.g. in fluorite (CaF2) there is one
cation and two anions so n = 1 + 2 = 3.

lattice A CN stoich A/n


CsCl 1.763 (8,8) AB 0.882
NaCl 1.748 (6,6) AB 0.874
Zinc blende 1.638 (4,4) AB 0.819
wurtzite 1.641 (4,4) AB 0.821
fluorite 2.519 (8,4) AB2 0.840
rutile 2.408 (6,3) AB2 0.803
CdI2 2.355 (6,3) AB2 0.785
Al2O3 4.172 (6,4) A2B3 0.834

Notice that the value of A is fairly constant for each given stoichiometry and that the
value of A/n is very similar regardless of the type of lattice.
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Ionic Bonding
If only the point charge model for coulombic energy is used to estimate the lattice energy (i.e.
if U0 = Ecoul) the calculated values are much higher than the experimentally measured lattice
energies.
E.g. for NaCl (rNa+ = 0.97Å, rCl- = 1.81Å):

U0 = 1390 (zA zB / d0) * A = 1390 ((1)(-1)/2.78) * (1.748) kJ/mol = - 874 kJ/mol


But the experimental energy is -788 kJ/mol. The difference in energy is caused by the
repulsion between the electron clouds on each ion as they are forced close together. A
correction factor, Erep, was derived to account for this.
Erep = - (e2 / 4  0) * (zA zB d*/ d2) * A and since
Ecoul = (e2 / 4  0) * (zA zB / d) * A the total is given by
U0 = (e2 / 4  0) * (zA zB / d0) * A * (1-(d*/d0))

This is the Born-Mayer equation, when the constants are evaluated we get
the form of the equation that we will use:
U0 = 1390 (zA zB / d0) * A * (1 - (d* / d0)) in kJ/mol
Note: d* is the exponential scaling factor for the repulsive term and a value
that we will use for this is 0.345 Å.
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Ionic Bonding
Using the Born-Mayer equation, for our example with NaCl.

U0 = 1390 (zA zB / d0) * A * (1 - (d* / d0))

= 1390 ((1)(-1)/2.78) * (1.748) * (1-(0.345/2.78) kJ/mol = - 765 kJ/mol

Which is much closer to the experimental energy of -788 kJ/mol.

Kapustinskii observed that A/n is relatively constant but increases slightly with coordination
number. Because coordination number also increases with d, the value of A/nd should also be
relatively constant. From these (and a few other) assumptions he derived an equation that does
not involve the Madelung constant:
Kapustinskii equation :
U0 = (1210 kJ Å / mol) * (n zA zB / d0) * (1 – (d* / d0))

One advantage of the Kapustinskii equation is that the type of crystal lattice is not important.
This means that the equation can be used to determine ionic radii for non-spherical ions (e.g.
BF4-, NO3-, OH-, SnCl6-2 etc.) from experimental lattice energies. The self-consistent set of radii
obtained in this way are called thermochemical radii.
Solid State Physics Dr. rer. nat. Muldarisnur 30
Covalent bond
Non-metal elements usually just need one or two electrons to fill their
outer shells. So how do they form a bond?

incomplete
Cl outer shells Cl

The two non-metal atoms cannot form a bond by transferring electrons


from one to another. Instead, they share electrons.

Each atom now has


Cl Cl a full, stable outer
shell.

The shared electrons join the atoms together. This is called a covalent
bond.
Solid State Physics Dr. rer. nat. Muldarisnur 31
Covalent Bond
 When the electronegativity between two atoms is small, the two atoms
can form covalent bond by sharing a pair of electrons (one from each
atom).
 e.g. Si, Ge, Diamond, Graphene, carbon nanotube, fullerene
 For two atoms with orbital wavefunctions:  1 , 2
 The molecular orbital of the two atoms are linear combinations of  1
and  2
 b   1  2
 a   1  2

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What are the types of covalent bonds?

Solid State Physics Dr. rer. nat. Muldarisnur 33


Can compounds contain covalent bonds?
 Covalent Bond can also occur between atoms of different non-
metals to create molecules of covalent compounds. These covalent
bonds can be single, double or triple.
 How is a covalent bond formed in hydrogen chloride (HCl, also
represented as H–Cl)?

H Cl H Cl

 Hydrogen and chlorine both need one more electron to fill outer
shells. By sharing one electron each, they both have a stable outer
shell and a covalent bond is formed.
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Covalent Bond in water
 Compounds can contain more than one covalent bond.
 Oxygen (2.6) needs 2 more electrons, but hydrogen [1] only needs
1 more. How can these three elements be joined by Covalent
Bond?
 The oxygen atom shares 1
electron with 1 hydrogen
atom, and a second electron O
with another hydrogen H H
atom.

 What is the name of the molecule that is formed?

 H2O (or H–O–H) is water.

Solid State Physics Dr. rer. nat. Muldarisnur 35


Polar Covalent Bonds

Though atoms often form


compounds by sharing
electrons, the electrons are
not always shared equally.

 Fluorine pulls harder on the electrons it shares with hydrogen


than hydrogen does.

 Therefore, the fluorine end of the molecule has more electron


density than the hydrogen end.

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Electronegativity
Electronegativity is the ability of atoms in a molecule to attract electrons
to themselves.

Higher
electronegativity
means greater
electron attraction
to that atom

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Electronegativity Difference and Bond Type
 If the difference in electronegativity between bonded atoms
is 0, the bond is pure covalent.
 Equal sharing

 If the difference in electronegativity between bonded atoms


is 0.1 to 0.4, the bond is nonpolar covalent.

 If the difference in electronegativity between bonded atoms


is 0.5 to 1.9, the bond is polar covalent.

 If difference in electronegativity between bonded atoms is


larger than or equal to 2.0, the bond is ionic.

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Electronegativity Difference and Bond Type

Solid State Physics Dr. rer. nat. Muldarisnur 39


Metallic Bonding

 All pure metals have metallic bonding and therefore exist as


metallic structures.
 Metallic crystal consists of a regular arrangement of positive ion
cores of the metals surrounded by a mobile delocalized sea of
electrons.
 Metallic bond is caused by the electrostatic force of attraction
between positively charged ions & delocalized valence electrons.
Solid State Physics Dr. rer. nat. Muldarisnur 40
Metallic Bonding
 Each atom donates its valence electrons to the whole.
 Valence electrons are delocalized. Shared by all atoms in the
material
 Electrons are free to drift throughout the material
 Atom therefore becomes a cation (here called an ion core)
 Donated electrons form an electron cloud surrounding all the ion
cores
 Electron cloud binds all the ion cores together by coulombic forces

 unique properties only found in metals


 shiny metallic luster
 good electrical and thermal
conductivity
 many others ...

Solid State Physics Dr. rer. nat. Muldarisnur 41


Intermolecular Force

Classification diagram of intermolecular forces

Solid State Physics Dr. rer. nat. Muldarisnur 42


The Origin of Intermolecular Forces
It is weak electrostatic force of
attraction that exist an area of
negative charge on one
molecule and an area of positive
charge on a second molecule.

 What causes intermolecular forces?


Molecules are made up of charged particles: nuclei and electrons.
When one molecule approaches another, there is a multitude of
interactions between the particles in the two molecules.

 Each electron in one molecule is subject to forces from all the


electrons and the nuclei in the other molecule.
Solid State Physics Dr. rer. nat. Muldarisnur 43
Intermolecular Forces
 Intermolecular force is weak compared to covalent bond. It is
relatively weak interactions that occur between molecules.

 There are 2 types of intermolecular forces (both of them are


electrostatic attraction between dipoles formed by uncharged
molecules.)
1) Van der Waals' force
2) Hydrogen bonding

 Van der waals’ force is formed by dipoles. There are 3 types of


dipoles:
1) Permanent dipoles
2) Instantaneous dipoles
3) Induced dipoles

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Van der Waal’s
Van der Waals Interaction: arises from interaction between dipoles
 Fluctuating dipoles
asymmetric electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
Callister & Rethwisch 8e. bonding

 Permanent dipoles-molecule induced


secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding
H Cl

-ex: polymer
secondary bonding

Solid State Physics Dr. rer. nat. Muldarisnur 45


Dipole-Dipole Interactions

 Molecules that have permanent dipoles are attracted to each other.


 The positive end of one is attracted to the negative end of the other
and vice-versa.
 These forces are only important when the molecules are close to
each other.
Solid State Physics Dr. rer. nat. Muldarisnur 46
Permanent Dipole
These molecules have a permanent separation of positive and negative
charge.
A simple example is HCl

+ -

 The pair of electrons in the covalent bond between hydroge and


chlorine is unequally shared due to the difference in electronegativity
between hydrogen and chlorine.
 Chlorine has a greater electronegativity compared to hydrogen and
hence Chlorine tends to attract the bonded electron pair to itself.
 Chlorine becomes slightly negatively charged (-), hydrogen atom has a
partial positive charged (+) .
 The unsymmetrical distributed charge on the HCl molecule produces a
permanent dipole.
Solid State Physics Dr. rer. nat. Muldarisnur 47
Instantaneous Dipole
 Instantaneous dipole is due to the fluctuation of electron clouds
on non-polar molecules, positive and negative charges exist
temporarily.
 Also known as London forces or Dispersion Forces
 Instantaneous dipole-induced dipole Interactions exist in non-
polar molecules.
 These forces result from temporary charge imbalances. The
temporary charges exist because the electrons in a molecule or
ion move randomly in the structure.
 The nucleus of one atom attracts electrons form the neighboring
atom. At the same time, the electrons in one particle repel the
electrons in the neighbor and create a short lived charge
imbalance.
 These temporary charges in one molecule or atom attract
opposite charges in nearby molecules or atoms.
Solid State Physics Dr. rer. nat. Muldarisnur 48
Induced Dipole
Induced dipole exists when a permanent dipole or
instantaneous dipole comes close to a non-polar molecule, the
non-polar molecule will be induced to form a dipole temporarily.

Solid State Physics Dr. rer. nat. Muldarisnur 49


Van Der Waals Bonding
 A WEAK dipole-dipole interaction is the origin of the Van der Waals
bond, which is therefore characterized by a LOW cohesive energy, &
so LOW melting temperatures

Coulomb attraction can occur between


+ - + - two neutral spheres, as long as they
have some “internal charges” so that
the neutral spheres can be polarized
 Also, spontaneous dipole formation in one atom may induce an
equal & opposite dipole in another atom nearby, causing attraction
between them through the dipole dipole interaction.
 Another type of van der Waals bonding is observed for certain
\POLAR molecules that have a PERMANENT dipole moment
Solid State Physics Dr. rer. nat. Muldarisnur 50
Van Der Waals Bonding
 Although atoms are electrically NEUTRAL, the electrons within
them are in a constant state of motion, and so may MOMENTARILY
form small electric DIPOLES.

 The direction & magnitude of these dipoles are constantly


fluctuating, but may INDUCE similarly fluctuating dipoles in other
atoms.

+e -e

+ -

Solid State Physics Dr. rer. nat. Muldarisnur 51


Van Der Waals Bonding
The Van der Waals potential energy can be APPROXIMATED as:

2nd term = classical


A B
E (r )  n  m dipole-dipole interaction  r-6.
r r 1st term = repulsion for small r.
Typically people use
A & B are empirical
n = 12, m = 6
parameters, as is n

At equilibrium , we have
1
dE  nA  nm B m 
 0  ro   & E (ro )   1
 mB 
m 
dr r ro ro  n 

ro and E(ro) are the equilibrium SEPARATION and ENERGY


For a stable bond to form E(ro) must be NEGATIVE thus m < n
Solid State Physics Dr. rer. nat. Muldarisnur 52
Van Der Waals Bonding

A B
E (r )  n  m
r r
dE nA mB
 0   n 1  m 1
dr r  ro r r
nA mB mn mB
n 1
 m 1  r 
r r nA

1
 nA  nm B m 
ro    & E (ro )  m  n  1
 mB  ro  

Solid State Physics Dr. rer. nat. Muldarisnur 53


Hydrogen Bondıng
 A H atom has only 1 electron, so it can be covalently bonded to
only one other atom.
 However, the H atom can involve itself in an additional electrostatic
bond with a second H atom of highly electronegative character
such as F or O.
 This 2nd bond permits a Hydrogen Bond between two atoms or
structures.

 The hydrogen bond strength


varies from 0.1 to 0.5 eV/atom.

Solid State Physics Dr. rer. nat. Muldarisnur 54


Hydrogen Bonds
 Attractive force between electropositive hydrogen of one molecule
and an electronegative atom of another molecule
 Common between dipoles such as water
 Also act as intramolecular bonds, holding a large molecule in a three-
dimensional shape  +

–
Hydrogen bond
 The slightly positive ends (indicated by
(+) of the water molecules +
dotted line)
become aligned with the – +
–
slightly negative ends (–) of –
+ +
other water molecules.
+

–

Solid State Physics Dr. rer. nat. Muldarisnur 55


Comparison among Bond Types
intermolecular
Type of bonding metallic ionic covalent
forces
Type of elements Between metals Metals and nonmetals Between Between molecules
used nonmetals
Givers &/or takers of Between givers Between givers and Between takers
electrons takers
Description Valence e- roam freely Transfer e- Share e- Hold covalently
between many atoms bonded molecules
(delocalized). Sea of Makes (+) and Forms discrete together as a solid.
e- surrounding (+) (-) ions that are attracted molecules.
kernels. to each other.

Type of material Solid metallic Ceramics and glass Polymers and Helps form solid
formed elements and alloys some polymers
ceramics/glasses
Strength of bond Relatively strong Very strong Very strong Weak
Properties Good conductors, Brittle, Insulators, Help determine a lot
Produced workable, corrode high melt temps, don’t corrode of properties of
easily, generally high nonconductors as solids, covalent compounds
melt temps but don’t corrode (polymers). Soft and
variable plastic

Solid State Physics Dr. rer. nat. Muldarisnur 56


Comparison among Bond Types
Ionic Covalent Metallic Intermolecular
moderate and
Bond strength strong very strong weak
variable
low to moderate;
Hardness moderate to high very hard, brittle ductile, soft and plastic
malleable
conducts by ion good conductors;
Electrical insulator in solid insulators in solid
transport only by electron
conductivity and liquid and liquid states
when dissociated transport

Melting point moderate to high low generally high low

soluble in polar very low soluble in


Solubility insoluble
solvents solubilities organic solvents
diamond,
Cu, Ag, Au, other ice, organic
Examples most minerals oxygen, organic
metals solids (crystals)
molecules

Solid State Physics Dr. rer. nat. Muldarisnur 57


Bonding vs Properties

Types of
Bonding

Ionic Van Der Waals Metallic Covalent Hydrogen


Bonding Bonding Bonding Bonding Bonding

Very High Melting Low Melting Points


High Melting Variable Melting
Low Melting Point
Point Point
Points Soft and Brittle
Very Hard
Hard and Brittle Variable
Soft and Brittle Usually
Hardness
Usually not Non-Conducting
Non conducting
Non-Conducting Conducting
solid Conducting
İce,
Ne, Ar, Kr and Xe Diamond, organic solids
NaCl, CsCl, ZnS Fe, Cu, Ag
Graphite

Solid State Physics Dr. rer. nat. Muldarisnur 58


Binding Energies of Bonds

Energy Energy
Bond Type Energy (eV)
(kJ/mole) (kJ/mole)
Ionic ~5-15 (strong) ~500-1500 NaCl: 640
Diamond:
Covalent ~1-10 (strong) ~100-1000
~710
~0.5-8.5
Metallic ~50-850 Fe: 406
(strong)
Hydrogen ~0.05-1.5 ~5-155 H2O: 51
Van der Waals ~0.01-0.5 ~1-50 Ar:7.7

kBT ~ 0.026 eV at T = 300 K


Solid State Physics Dr. rer. nat. Muldarisnur 59
Model Ionic Lattice in 1 Dimension
… –- + -– + –- + –- + …
R  ()
Madelung const.  (rij  Rpij )
R j i
Rpij

The value of α is defined in terms of the lattice constant


R. Start on a negative ion, summing (left & right)
This sum is conditionally convergent! This means the order of the
terms in the sum matters!
() 1 1 1 1 
   j i  2      ...
pij 1 2 3 4 

 x 2
x 3
x 4 
Since ln(1 x)   x     ...   2 ln 2
 2 3 4 

Solid State Physics Dr. rer. nat. Muldarisnur 61


However, a concentric cube calculation does
converge:

Solid State Physics Dr. rer. nat. Muldarisnur 62

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