Ionic bond

Ionic Bond electrostatic interaction of oppositely charged ions

Example: NaCl (sodium chloride)

positive and negative ions
arrange by:

Coulomb attraction: between ions of opposite sign

Coulomb repulsion: between ions of same sign

Repulsion more than compensated by

attraction
Closer look to energetic

+ 5.1 eV Na+ +
(ionization energy)

∞
Cl + - + 3.6 eV
Cl
(electron affinity)

Na+ + - Na+ - + 6.1 eV

∞
Cl Cl
r0 (electrostatic energy)

-0.3 eV (Pauli repulsion)

 + Cl - + 4.3 eV=
Na+ Cl (6.1-0.3)eV-5.1eV+3.6eV
r0
(dissociation energy)

How to find r0 ?
 1 e2
Ei  ECoul  Erepuls   B exp(r / ) minimum
40 r

Click for reference and additional

information
From a single Na+Cl- bond
to the NaCl solid

r0 2

r0

Neither contact between cations (Na+ ) nor contact between anions (Cl- )

apart from nearest-neighbor interaction only Coulomb terms

involved
Na+ has: 6 Cl- nearest neighbors at distance r0

12 Na+ next nearest neighbors at 2 r0

8 Cl- further neighbors at distance 3 r0

3 r0
r0

2 r0
 Total Coulomb energy per ion pair: Ecoul

Madelung Constants
Ecoul= E( 6 Cl nearest neighbors at distance r ) + E( 12 Na
-
0
+
nearest neighbors at distance 2 r0 )
+ E( 8 Cl- at distance 3 r0 )+…

 e2  12 8 
Ecoul   6    ...
40r0  2 3 

Erwin Rudolf Madelung

 e 2 1881-1972
Ecoul  where α=1.748 is the Madelung constant
40r0
12 8
Series   6    ... slow convergence
2 3
methods for accurate sums
Ewald (1921) and Evjen (1932)
alternating sign
Madelung Constants

(Data from Handbook Menu )

Compound Crystal Lattice M

NaCl NaCl 1.74756
CsCl CsCl 1.76267
CaF2 Cubic 2.51939
CdCl2 Hexagonal 2.244
MgF2 Tetragonal 2.381
ZnS (wurtzite) Hexagonal 1.64132
TiO2 (rutile) Tetragonal 2.408
bSiO2 Hexagonal 2.2197
Al2O3 Rhombohedral 4.1719
 Total energy per ion pair: Ei=ECoul+ERepulsive

  e2
Ei   C e r/
4 0 r
t ers
r ame
a
np
dEi now
However: condition 0 un
k
dr r=r
0

dEi  e2 C r0 / 
determination of,e.g., C   e 0
dr r r0 4 r 2 
00
e2 r0 /    e2
C e Ei   C er /  r0 r 
40r0 2 40r  2
 e  r
Ei  1 2 e  
40r  r0 
 
  e 2    ?
Ei @ r=r0 Ei  1 
40r0  r0  Input from
experiment
Click here for response functions in gases.
Note that the bulk modulus B is inverse proportional to the bulk compressibility 

1 dV
bulk compressibility    since NaCl cubic  xx   yy   zz  
V dp

corner shared amog 8 adjacent cubes

1/8 (4Na+ +4Cl-)=1/2 NaCl

1 NaCl-molecule requires

V  2 r 3 ̂ +
r
 Click for details. Note special sign convention in thermodynamics

work W=pdV related volume change

d(2r 3 ) dE  dUT 0
dV  dr  6r 2dr
dr
  dW  p dV
pF/ A dV  A dx
dp dp d 2E d 2E
Aim: 
 and 
 2 
dr dr dr dr 2

dE dE dr 1 dE dp d  1 dE  1 d2E 1 dE
p   2   2    
dV dr dV 6r dr dr dr  6r dr  6r 2 dr 2 3r 3 dr
dr 1 1  d2E 
 2  dp 
dV 6r    2 2
 dr  r r0 6r0  dr  r r
0
Let´s remember

1 dV 1 dV dr 6r 2 dr 3 dr  dp  3
   3     
V dp V dr dp 2r dp r dp  dr  r r0 r0 

 d2E  18r0
 2 
 dr  r r0 
  2  2
r0 r   
18r0  d E  2
d  e  r
 2  2 1 2 e    
  dr  r r0  dr  4 0r  r   
 0    r r0
 

 1

r0 720 r0 4 Cohesive energie
2
 e2 (can be experimentally determined via Born-Haber cycle)
Click for detailed information

Properties of ionic crystals

o
  0.345 A  0.0345nm for all alkali halides Mott and Gurney 1948

However: widely varying values of C in the repulsive term ?

closed-shell ions behave like incompressible spheres
take into account different radii according
r ra rc  r

 
(alkali)+ (halogen)- C e  C e universal C´ for all alkali halides
Ionic Sizes
Completely ionic bond is an ideal case

In general bond neither covalent nore pure ionic Mixed ionic-covalent bonds
  cov   ion

  Ĥd
 determined from E  Min.
   d

Paulings concept of electronegativity Semi-quantitative estimation of λ

Electronegativity refers to the ability of an atom in a

molecule to attract shared electrons.

δ+ δ-

A + B A B
 δ+ δ- 1/2

E( A B ) > [E( A A )  E( B B )]

because there is Coulomb interaction between δ+und δ-

empirical formula

E( AB)  E( AA )  E(BB)  1.3eV ( A  B ) 2

1
better than  E( AA )  E(BB)
2

Linus Pauling
is the only person ever to receive two unshared Nobel Prizes
—for Chemistry (1954) and for Peace (1962).
Find here Pauling’s electronegativity
online
 2
% ionicity of bond  100
1  2

determined from dipole moment of molecules  A  B

  A  B

  A B  
   
2
 2  
% ionicity of bond  1001  e


 