Chapter 22.

Intermolecular interactions
Atoms and molecules, even uncharged ones, are attracted to each other

1
Chapter 22. Intermolecular interactions

du (r )
f (r )  
dr

u (r ) - pair potential

f (r ) - force between two particles

r * - equilibrium bond length

u (r )  r  p p is positive integer
p3 short range interaction
p3 long-range range interaction (Coulombic)

2
Chapter 22. Intermolecular interactions

3
Chapter 22. Intermolecular interactions
multipoles

 ( x, y , z ) Multipole expansion

  ( x, y, z )dV monopole

 r  ( x, y, z )dV dipole

4
Chapter 22. Intermolecular interactions
Permanent dipole
depends on symmetry

CO2

H2O

5
Chapter 22. Intermolecular interactions

interaction Distance dependence

Ion-ion 1/r
Ion-dipole 1/r2
Dipole-dipole 1/r3
Dipole-induced dipole
Two rotating dipoles 1/r6
London

6
Chapter 22. Intermolecular interactions
Orientation averaging shortens the range of interactions

1
u (r )  charge-fixed dipole
r2

1
u (r )  charge-free to rotate dipole
r3

1
u (r )  fixed dipoles
r3

1
u (r )  free to rotate dipoles
r6

7
Chapter 22. Intermolecular interactions
London dispersion forces

Attractive interaction are universal. Two molecules can induce an attraction in each
other because they are polarizable

ind   E

 polarizability

1 2
u (r )  
r6

8
Chapter 22. Intermolecular interactions
London dispersion forces

Attractive interaction are universal. Two molecules can induce an attraction in each
other because they are polarizable

ind   E

 polarizability

1 2
u (r )  
r6

 C 2Q 2
u (r )  
2D2r 4 9
Chapter 22. Intermolecular interactions
Lennard-Jones potential

a b
u (r )  
r12 r 6

10
Chapter 22. Intermolecular interactions
Hydrogen bonds

Weak interactions that occur when a hydrogen atom is situated between two other atoms

11
Chapter 22. Intermolecular interactions
Hydrogen bonds

Weak interactions that occur when a hydrogen atom is situated between two other atoms

12
Chapter 22. Intermolecular interactions
Empirical energy function

13
Chapter 22. Intermolecular interactions
The van der Waals gas model

NkT
p Ideal gas
V
NkT aN 2  kT
p  2   a 2 van der Waals equation of state
V  Nb V 1  b

14
Chapter 22. Intermolecular interactions

NkT aN 2
p  2 van der Waals equation of state
V  Nb V

kT a
p  1/2 1 Redlich-Kwong equation
V  b1 T V (V  b1 )

15
Chapter 22. Intermolecular interactions

U   u (r )  g (r )4 r 2 dr
0

  N /V

g (r ) radial distribution function

pair correlation function

16
Chapter 22. Intermolecular interactions
Nearest-neighbor


N
U
2
 u
r 0
( r )  g ( r )4 r 2

1
u (r ) 
r6


N N Nwz
U
2
 u
r 0
( r )  g ( r )4 r 2

2
u (r*) z 
2

 (1/ r ) 4
( 4 / 90)  1
r 2
  0.076

( / 90)
4

 (1/ r )
r 1
4

17
Chapter 22. Intermolecular interactions
Take home message

interaction Distance dependence

Ion-ion 1/r
Ion-dipole 1/r2
Dipole-dipole 1/r3
Dipole-induced dipole
Two rotating dipoles 1/r6
London

a b
u (r )   Lennard-Jones potential
r12 r 6

NkT aN 2
p  2
V  Nb V van der Waals equation of state
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Chapter 22. Intermolecular interactions
Take home message

19