QUANTUM OR WAVE MECHANICS

Quantum chemistry mathematically describes the fundamental behaviour of matter at

the molecular scale.

Normal chemical reactions are actually the flow of electrons between atoms or
molecules
Na + Cl  NaCl  Na+ + Cl

Knowledge of the energy and position of electrons helps us understanding chemical

reactions and also the structures of different molecules.

The particle property of electrons:

22 e' 4 Z 2  e' 4 Z 2  e 4Z 2 18 Z

2
En       2.17868 x 10
n 2h 2 2n 2 2 8h 202 n2
 n=7 E7
n=5 E5
n=5 E5

En n=4 E4
er
n=3 E3 = -1.4 eV
gy

n=2 E2 = -3.4 eV

n=1 E1 = -13.6 eV
1. Calculate the groundstate energy of the hydrogen atom and convert the
result to electron volts. 1 eV = 1.602177 x 10-19 J. (Answer: -2,17868 x 10-18 J
= -13.568 eV. This is the minimum energy needed to ionise a ground-state
hydrogen atom)

2. Calculate the energy required to excite the hydrogen electron from an energy
level n = 1 to n = 6 (Answer: 2.118 x 10-18 J)

3. Calculate the wavelength of light that must be absorbed by a hygrogen atom

in its ground state (n = 1) to reach the first excited state (n = 2). (Answer:
1.217 x 10-7 m)
 Electron waves:

c  = “nu” = frequency in s-1 or Hz (hertz)

  c = velocity of electromagnetic waves = 3 × 108 ms-1

 = wavelength

Derivation of de Broglie equation:

hc h = 6,62608 x 10-34 J s
E  h  Planck’s constant, c = 3 × 108 m s-1

hc c h
E = mc2 E  h   mc 2 or λ = 
  mc

h h h
   
mc mv p

Compare the wavelength for an electron (mass 9.11 x 10-31 kg) travelling at a speed of
1.0 x 107 m s-1 with that for a ball (mass 0.10 kg) travelling at 35 m s-1. (Answer: e =
7.3 x 10-11 m; b = 1.9 x 10-34 m)
Heisenberg’s uncertainty (indeterminacy) principle:

Our concepts of mass, position, velocity, momentum and energy is derived from
experience with the mechanical behaviour of relatively large macroscopic bodies
and we can describe the behaviour of such bodies to our satisfaction in terms of
these concepts. When used in the description of the very small particles
involved in atomic systems, however, the quantities defined by these concepts
cannot be measured with equally satisfactory certainty. Any observation or
measurement we make necessitates some interaction with the system being
studied. For example, when the position of an object is observed, there is no
avoiding the impingement of light upon it or it being touched by some other
object. The measurement itself therefore influences the system under
observation and introduces an uncertainty in the validity of the measurement.
h
(x)(p) 
4
 x


  assume 
x
p h
p  p  
x x
x p   h  Planck' s constant
 6.624 x 10 34 J s
Wavefunctions in describing p en x of an electron:

Since an electron has wave properties, it’s behavior is described as a wave

function, or (x, y, z), the latter meaning that  is a function of co-ordinates x,
y and z. The wave function can take on positive, negative, or imaginary values.
The probability of finding an electron in any volume element in space is
proportional to the square of the absolute value of the wave function,
integrated over that volume of space.

An example of a wave function describing the behavior of electrons is

2x
ψ = A sin . The probability of finding an electron with wavelength λ

(momentum p = h/) at position x is proportional to A2: probability  A2.
The general wave-equation:

2x
 (x ) = A sin and  (t )  A sin 2   t are used to derive the

general wave equation.

+y

-y

Y(t) A t
 y = A sin 2 t =  ( t ) with A = amplitude = maximum value of y
and  = frequency = number of cycles per second measured in s-1 = Hz

Y(x) x

x c
The velocity c = in the wave property   can be displaced with
x t x 
v= =  , therefore t =
t 

x = A sin 2  x
 (x) = A sin 2
 
 2 x
 ( x, t ) =  ( x) .  (t ) = A sin  A sin 2  t

2x
 (x ) = A sin and  (t )  A sin 2   t

d (sin x)
  2  2 x   cos x
  A cos  (t ) dx
x    
d cos x
  sin x
 
2
 4 
2
2 x   4 2
dx
  A sin  t    ( x) (t )
 x2  
2
   2 d sin kx
 k cos kx
dx
 d cos kx
  k sin kx
=  x 2 A cos 2t  dx
t

2
   x   4 2 2  A sin 2 t    ( x)  4 2 2  (t )
t 2
 2
x2 1 1 2 1 2
   
 2  
2 2
c2 x2 c2 t 2
t 2

1 2
  
2

c 2
t 2
  
met 2    ,   del.
x 2
y 2
z 2

2  2  2  2  1 2 
    2  with   ( x , y , z, t )
r 2
x 2
y 2
z 2
c t 2
Derivation of the time-independent Schrödinger equation in one dimension:

 ( x, t )   ( x)  (t )   ( x)  A sin 2 t

  ( x)
  A sin 2  t
x x

2  2 ( x)  2 x 
  A sin 2 t    t 
x2 x 2
x 2


  ( x)  2 A cos 2 t 
t

2
  ( x)   4 2 2
 A sin 2 t 
t 2
  4 2 2 ( x) (t )
 2 1  2
 
 x2 c2 t2

 2 ( x)
  t  
 1

 2    4 
2 2

   x   t 
x 2
c 

 2 ( x) 4 2 2 c
   ( x)  0  
 x2 1c 2 

 2 ( x) 4 2
   ( x)  0
x2  2
  h E = KE + PE
   
 p  1
= mv 2  PE
2
2 2
= m v  PE
2m
2
= p  PE
2m
1

 p  2mE  PE  2
 2 ( x) 8 2 m
1  E  PE  ( x)  0
 h2m E  PE 
h
  2
x2 h2
p
1  2m E  PE  8 2 m
OR     2
 E  PE   0
2
 h2  h2

 h2
  2  U  E
8 m
2
The Hamilton operator H: H  E

 h2
H   2
 U
8 2 m

d d
   E   e nx
dx dx

d
 ne nx  n
dx

d d
If   e is a solution of
nx
 E , it follows from  n
dx dx
that E = n, in other words Eigenvalue = n for the eigenfunction   e nx
 Relationship between the total energy and amplitude:

Consider the ball hanging from a spring. Hook's law states F(x) = -Kx with K =
constant of spring, x = displacement, F = force exerted on or by the spring.
If the spring is stretched and the ball moves, the following hold:
At x = 0 the PE = 0 and KE = max = 1 mv 2 . At x = A the PE = max = -Kxmax and
2
KE = 0. Therefore the total energy E of the spring: E  KE  PE
 0  PE maks if (x = A)
1
but PE (x) 
 F x  dx  Kx dx  
x x

0
 0 2
Kx 2

1  1 
Therefore E  PE maks   Kx 2    KA 2  or E  A2
2  x mak s  A 2 
 Solution of the time-independent Schrödinger equation of a particle in
a one- dimensional box:

d 2  x  8 2 m
 E   x   0
d x2 h2
n x
 n x   A sin 0  x  

 0 x  0, x  
n  1, 2, 3...
  n  x   n  n x 18
  A  cos
x    
E4 = 16h2/8ml2
 2 n  x 
16
 n  n x
2

  A   sin
x2     14

 n 
2

    n x  12
  

Energy levels
10
E3 = 9h2/8ml2
  n x   n 
2 2

    n x   0 8
x 2
  
6

n2 h2
En  4
E2 = 4h2/8ml2
8m  2
2
E1 = h2/8ml2

0
 18
18

16
16

14
14

12
12
Energy levels

Energy levels
10
10
2 2
E3 = 9h /8ml E3 = 9h2/8ml2
8
8

6
6

E2 = 4h2/8ml2 E2 = 4h2/8ml2
4
4

2
2
E1 = h2/8ml2 E1 = h2/8ml2
0
0
 18
18

16
E4 = 16h2/8ml2 E4 = 16h2/8ml2
16

14
14

12
12
Energy levels

Energy levels
10
10
E3 = 9h2/8ml2 E3 = 9h2/8ml2
8
8

6
6

E2 = 4h2/8ml2 E2 = 4h2/8ml2
4
4

2
2
E1 = h2/8ml2 E1 = h2/8ml2
0
0
 18
18 [Y4(x)]2
Y4(x)
E4 = 16h2/8ml2 16 E4 = 16h2/8ml2
16

14
14

Energy levels in h2/8ml2

12
Energy levels in h2/8ml2

12
[Y3(x)]2
Y3(x)
10
10
E3 = 9h2/8ml2
E3 = 9h2/8ml2
8
8

[Y2(x)]2
6
6
Y2(x)
E2 = 4h2/8ml2
4
E2 = 4h2/8ml2 4

[Y1(x)]2
Y1(x)
2
2
E1 = h2/8ml2
E1 = h2/8ml2
0
0 l /2 l
l /2 l 0
0
Electrons confined to a one-dimensional box
 (2/a)

Y3(x) or Y3(x) for energylevel E3

[Y3(x)]2

(2/a) 1/2

x = l /2 x= l
2

Y3(x) = (2/a)1/2sin3x/l

The three dimensional box with dimensions a x b x c:

b

a
 PE = 0 0<x<a 0<y<b 0<z<c
PE =  x  0, x  a y  0, x  b z  0, x  c

 2 2 2  8 2 m
 2  2  2  ( x, y, z )  2 ( E ) x, y, z   0
 x y z  h

n x h 2 n x2
 n x   A sin x with E x 
x
a 8m a 2
ny  y h 2 n y2
 n  y   B sin with E y 
y
b 8 mb 2
n z h 2 n z2
 n z   C sin z with E z 
z
c 8m c 2

n x ny  y n z
 x, y, z  =  x  y  z  = ABC sin x sin sin z with
a b c
= h  n x n 
2 2 2 2
Etot = E x  E y  E z n
 
y z

8m  a 2 b 2
c 
2
  n2 x  dx  1 and / en n x  is normalised

 0

 nx
0 A 2 sin 2

dx  1

A 2  2nx 
2  0
 1  cos
 
 dx  1

2  2
  
1
2nx 
A
x0   
 A 2 n
 sin   1
2  2      0
A 2  A 2  2n  
1

  
 sin 2n  sin 0   1
0

2  2    
A 2
 0  00  1
2
2
A2  or

1
 2 2
A   

 sin 2 x 
1
1  cos 2 x  1
2 nx
2
 n  x     sin
2

 cos x dx  sin x  

sin n  0

1
 cos kx dx  k
sin kx

 2 1  cos 2kxdx
1
 kx 
2
sin

1  1 
   
2 
x sin 2 kx
2k  0
 Three dimensional box:

 n  x, y , z    n  x   n  y   n  z 
x y z

nxx n yy nzz 2 2 2

 ABC sin sin sin with A ; B ; C
a b c a b c
8 nxx n yy nzz
 sin sin sin
abc a b c
h 2  nx2 n y nz2 
2

with E   
8m  a 2 b 2 c 2 

Degeneration:

b
 2  2 8 2 m
  E   0
x2  y2 h2
0 a
 with  =  x, y    x .   y  10

n yy
9

= 2 n xx 2
sin  sin E 22= 8h2/8ml2
a a b b 8

= 4 sin n xx sin n y y 7

ab a b
6

Energy levels
h 2  n x2 n 
2
and Etot =
Ex  E y  
y

8m  a 2 b 2 
5
E12=E21=5h2/8ml2

(x, y, z) = (x)(y)(z) 3

= 8 sin n xx sin n y y sin n zz 2 E11=2 h2/8ml2

abc a b c
1

h 2  n x2 n y n z2 
2

 Ex  E y  Ez   
0
Etot
8m  a 2 b 2 c 2 
 18
18

16 16h2/8ml2 16

14
14

12
12
Energy levels

Energy levels
E111
10 E211
10 E121
2 2
9h /8ml E122
E212
E221

8 E122
8 E222

6 6h2/8ml2 6

4
4
3 h2/8ml2
2
2

0
0
Solutions of the Schrödinger equation for the hydrogen atom:

Y(r, , ) = R(r) () ()

n the principal quantum number

l the angular momentum quantum number
ml the magnetic quantum number

Electromagnetic radiation:
Absorption of radiation by molecules:

Emolecule = Eelectronic + Evibrational + Erotational + Etranslational + other ways

hc hc h 2n 2
E  or   En 
 E 8ma2
 Butadiene, CH2 = CH - CH = CH2

18 18

16 16

14 14

12 12
Energy levels

Energy levels
10 10
E3 = 9h2/8ma2 E3 = 9h2/8ma2

8 8

6 6

E2 = 4h2/8ma2 E2 = 4h2/8ma2
4 4

2 2
2 2
E1 = h /8ma E1 = h2/8ma2

0 0
 E  E excited  E groundstate H2C
C C 120
0

  h ng
 h 2 ne2 
2 2
120º C C
    0.5 x (1.54Å) 1
  8ma 2
2 
 8ma   
 h 2 C 2C 2120 H2C CH CH CH2
 C
0

   ne  n g
2  120º
 8ma  C 0.5 x (1.54Å) 1.35Å 1.54Å 1.35Å 0.5 x (1.54Å)

a = (C - C bond length distance) + 2(C = C bond length distance) + 2(0.5 x C-C

bond length distance for C orbital at end of molecule)

a = 1.54 Å + (2 x 1.35 Å) + (2 x 0.5 x 1.54 Å) = 5.78 Å = 5.78 x 10-10 m

8cma 2
 
h( ne  n g )
2 2

8  3 10 8  9.11  10 31  (5.78 10 10 ) 2


6.6226  10 34 [(3) 2  (2) 2 ]
 2.20 x 10 7 m or 220nm