FISIKA ZAT PADAT
FIS62114-FISIKA-KLS A
SEMESTER GENAP 2022/2023
BONDING IN CRYSTALS Dr. Sri Handani, M. Si.
INTERATOMİC BİNDİNG
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
ENERGİES OF INTERACTİONS
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
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.
VALENCE ELECTRONS
8A
1A
2A 3A 4A 5A 6A 7A
Number of valence electrons is equal to the Group
number.
WHY DO ATOMS FORM
BONDS?
ENERGİES OF INTERACTİONS
THE POTENTIAL ENERGY OF INTERATOMIC INTERACTION
ENERGİES OF INTERACTİONS
LENNARD-JONES POTENTIAL
LENNARD-JONES POTENTIAL: NOBLE GAS ATOMS
LENNARD JONES POTENTIALS
EXAMPLE – LENNARD-JONES (LJ) CLUSTERS
CHEMICAL BOND
ELECTRONEGATIVITY VS BOND TYPE
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
1 2
Primary Atomic Bonding Secondary Atomic Bonding
Ionic Covalent Metal Van Der Waals Hydrogen
Dipole - dipole
Polar Non Polar
Dipole – non dipole
Dispersive Force (London)
Classification of Solids by Atom Type & Type of
Bonding
This chart continues on the next!
Classification of Solids by Atom Type & Type of
Bonding
The chart on the previous page :
TYPES OF PRIMARY BONDS
Ionic : Electrostatic
attraction between ions.
Covalent : Sharing of
electrons.
Metallic : Metal atoms
bonded to several other
atoms.
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
IONIC BONDS
IONIC BONDS
Ionic bonds are formed by the attraction of oppositely charged ions.
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.
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 e0) * (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
IONIC BONDING
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 e0) * (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 e0) * (zA zB / d) * A
Note that the value of Ecoul must be negative for a stable crystal lattice.
I ONI C B ONDING
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.
IONIC BONDING
IONIC BONDING
COVALENT BOND
COVALENT BOND
WHAT ARE THE TYPES OF
COVALENT BONDS?
CAN COMPOUNDS CONTAIN COVALENT BONDS?
COVALENT BOND IN WATER
POLAR COVALENT BONDS
ELECTRONEGATIVITY
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.
ELECTRONEGATIVITY DIFFERENCE AND BOND TYPE
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.
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 ...
INTERMOLECULAR FORCE
Classification diagram of intermolecular forces
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.
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
VAN DER WAAL’S
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.
PERMANENT DIPOLE
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.
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.
Instantaneous Dipole-Induced Dipole interactions
Instantaneous Dipole-Induced Dipole interactions
VAN DER WAALS BONDING
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
+ -
VAN DER WAALS BONDING
VAN DER WAALS BONDING
H Y D R O G E N B O N D I N G
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.
HYDROGEN BONDS
Attractive force between electropositive
hydrogen of one molecule and an
electronegative atom of another molecule +
Common between dipoles such as water –
Hydrogen bond
Also act as intramolecular bonds, holding a large (indicated by
+ dotted line)
molecule in a three-dimensional shape
– +
–
+
–
+
The slightly positive ends
+
(+) of the water molecules –
become aligned with the
slightly negative ends (–) of
other water molecules.
COMPARISON AMONG BOND TYPES
Type of bonding metallic ionic covalent intermolecular forces
Type of elements used Between metals Metals and nonmetals Between nonmetals Between molecules
Givers &/or takers of Between givers Between givers and takers Between takers
electrons
Description Valence e- roam freely Transfer e- Share e- Hold covalently bonded
between many atoms molecules together as a
(delocalized). Sea of e- Makes (+) and Forms discrete solid.
surrounding (+) kernels. (-) ions that are attracted to each molecules.
other.
Type of material formed Solid metallic elements and Ceramics and glass Polymers and some Helps form solid polymers
alloys ceramics/glasses
Strength of bond Relatively strong Very strong Very strong Weak
Properties Good conductors, Brittle, Insulators, Help determine a lot of
Produced workable, corrode easily, high melt temps, don’t corrode properties of covalent
generally high melt temps nonconductors as solids, compounds (polymers).
but variable Soft and plastic
don’t corrode
COMPARISON AMONG BOND TYPES
Ionic Covalent Metallic Intermolecular
moderate and
Bond strength strong very strong
variable
weak
low to moderate;
Hardness moderate to high very hard, brittle
ductile, malleable
soft and plastic
conducts by ion good conductors;
Electrical insulator in solid insulators in solid
transport only by electron
conductivity when dissociated
and liquid
transport
and liquid states
Melting point moderate to high low generally high low
soluble in polar very low soluble in organic
Solubility solvents solubilities
insoluble
solvents
diamond, oxygen, Cu, Ag, Au, other ice, organic solids
Examples most minerals
organic molecules metals (crystals)
BONDING VS PROPERTIES
BINDING ENERGIES OF BONDS
Bond Type Energy (eV) Energy (kJ/mole) Energy (kJ/mole)
Ionic ~5-15 (strong) ~500-1500 NaCl: 640
Covalent ~1-10 (strong) ~100-1000 Diamond: ~710
Metallic ~0.5-8.5 (strong) ~50-850 Fe: 406
Hydrogen ~0.05-1.5 ~5-155 H2O: 51
Van der Waals ~0.01-0.5 ~1-50 Ar:7.7
MODEL IONIC LATTICE IN 1 DIMENSION
HOWEVER, A CONCENTRIC CUBE CALCULATION
DOES CONVERGE:
