2.

#Atomic#bonding#
!

Due!to!energy!minimization!of!the!electrons!when!atoms!come!into!
proximity!
The!outermost!electrons!play!the!dominant!role!in!bonding!
Consequence!of!electrostatic!interactions!between!nuclei!and!electrons!
obeying!Schrdingers!equation.!

Interatomic!potential!U!(arb.!Units)!

!
Interatomic!forces!are!made!up!of!an!attractive!and!repulsive!part.!!
!
!
R!
!
PauliEprinciple!

!
!
!
!
!
!
!
!
!
!
!
!
!

!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!Interatomic!distance!R!
!
!
Useful!classification:!!
!
E!! Ionic!
!
! E!! Covalent!
!
! E!! Metallic!
!
! E!! van!der!Waals!
!
! E!! Hydrogen!
!
!
2.1# Ionic#bonding#
#
Ionization!energy:!energy!to!remove!an!electron!from!a!neutral!atom!
!
Electron!affinity:! energy!gained!when!an!additional!electron!is!added!to!a!
neutral!atom!
!
Ionic!bonding!occurs!when!an!element!with!low!ionization!energy!is!combined!
with!an!element!with!high!electron!affinity.!(table)!
!
n!
n!
+
E!
!
F!

!
Example:!
!
!

Na!

5.14!eV!

Na+!

!Ionization!energy!

!
!

eE!

!!

!
!

eE!
!
!
!

ClE!

Cl!

3.61!eV!

!
!

!Electron!affinity!
!

Na+!

ClE!

Na+!

ClE!

!"

7.9!eV!

!
Energy!gain:!7.9E5.14+3.61=6.37!eV!
!
(1eV1.610E19!J)!
!
i!
i!
!
!
!
!
strength
range
!
!
!!"
!!
Potential:!!!" = ! + !"#$
! !!!!!!!!!!!!!!!!!!!!

!
!
!

this number is from Kittel,

Hofmann has 5.1eV calculated
from the Coulomb potential only.

q = e/ (4pi eps_0)

!
Coulomb!
empirical!
!
interact
repulsive!part
!
!
!
!
!! = !!! !!" !
j
!
!
!!" = !!" !!
!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! 2!
R:!nearest!neighbor!separation!
!
pijR
Pij:!depends!on!atomic!arrangement!
!

pijR
R

!
Only!include!repulsive!interaction!for!nearest!neighbor:!
!
!!
!"#$ ! ! ! !!!(!"#$"%&!!"#$!"#)
!
!!" =
!
!
1 !

!!!!(!"!"#$%!)
!!" !
N is the total number of ion pairs in the crystal,
!
e.g. Avogadros number for one mole.
!
!
!!"! = !!! = ! !"! !

!! !
!

!!!!!!with!!!!!!!!!!!! =

!!

!"

!
Number!of!nearest!
Madelung!constant!(depends!
!
neighbors!
!
on!atomic!structure)!
!
!
!
!!
Equilibrium!separation!R0:! !"!"! = 0!!(minimum!in!potential!diagram)!
!
!
Cohesive!energy!(lattice!energy):!Utot(R0)(
(
(
Cohesive!Energy!(lattice!energy):!Energy!that!must!be!added!to!the!crystal;!to!
separate!its!components!into!neutral!free!atoms/molecules!(ions)!at!rest.!
!
Typical!binding!energies!~8eV!
Not!directed!bond!
!
#
2.2# Covalent#bonding#
#
Atoms!share!electrons!
Positive!nuclei!are!attracted!to!electron!rich!area!
Electrons!are!localized!between!atoms!E>!directed!bonds!
PauliEexclusion!principle!results!in!bonding!of!antiEparallel!spins!
#

!
No!of!bonds!!"!No!of!valence!electrons!(unfilled!shells)!
!
Examples:!C,!Si,!Ge,!4!bonds,!tetrahedral!arrangement!(hybidisation)!
!
C!(diamond):!7.3!eV,!Si:!4.6!eV,!Ge:!3.87!eV!
!
!
!
2.3#Metallic#bonding:##
!
outer!electrons!removed!(atoms!with!low!ionization!energy),!but!no!
electronegative!ions!to!bind!them!
energy!gain!has!kinetic/potential!components!
non!localized!electrons!"!electrical!conductivity!
positive!ions!with!electron!fluid!!negatively!charged!glue!
!

Binding!energies:!~1E5!eV!(<!covalent!and!ionic!bonds)!
!
!
2.4#van#der#Waals#bonding:#
!
We!observe!bonding!between!inert!gases!with!completely!filled!electron!shells.!
Why?!
!

Charge!fluctuations!induce!dipole!moments!leading!to!attractive!forces!(Van!der!
Waals!or!London!force).!
!
[Always!present,!only!significant,!where!other!bonding!is!not!possible]!
!

!
!
!!"! =
!
!!"!

!!" (!)!
!!!!!"#$%!!"!!"#$%

1
= ! 4!
2

!
!!" !

!"

!
!!" !

!
!
Depends!on!atomic!arrangement!(crystal!structure)!
!
!
!
(!and!!can!be!determined!from!the!gas!phase!for!inert!gases)!
!
!!
Equilibrium!separation:!R0:! !"!"! = 0!!!
!
!
Examples:!!inert!gases!Ne,!Ar,!Kr,!Xe,!!
!
crystals!of!organic!molecules,!intermolecular!forces,!surface!tension,!
!
determines!shapes!of!giant!molecules!such!as!enzymes,!proteins,!and!
DNA!
!
Binding!energies:!~0.1!eV!!

!
2.5#Hydrogen#bonding#
#
#

!
!
H!bonded!with!strongly!electronegative!atom!(such!as!O)!
!
"!charge!distribution!leads!to!polarization!
"!electrostatic!forces!between!polarized!molecules!
!
!
Examples:!water,!ice!(density!anomaly),!responsible!for!linking!two!DNA!chains!
!
Binding!energies:!~0.1E0.3!eV!!
!
!
!
Many!bonds!are!intermediate!types!(covalent!!"!ionic)!(table)!
!
Some!structures!have!mixed!bonds,!i.e.!more!than!one!type!of!dominant!bond!
(for!example!graphite)!
Q: What are the different bonding types in graphite?
!
!
!
Question:!Why!is!salt!(NaCl)!brittle!and!iron!(Fe)!is!not!?!!
!
!
Computer!simulations:!
!
Molecular#dynamics#simulations:#
#
Calculating!Newtons!equations!of!motion!for!(large)!systems!of!particles!
"!based!on!interaction!potentials!
"!thermodynamic!properties!/!system!response!to!perturbations!
!

For a rigorous quantum basis for the above

concepts of bonding see
Bader, Richard (1994). Atoms in Molecules: A
Quantum Theory. USA: Oxford University Press.