QUANTUM
MECHANICS
Erwin Rudolf Josef Alexander Schrödinger
(1887 –1961)
one of the fathers of quantum mechanics,
the Schrödinger equation,
- he received the Nobel Prize in Physics in 1933.
In 1935,
after extensive correspondence with personal friend
Albert Einstein,
he proposed the Schrödinger's cat thought experiment.
The wave Equation ( Schrodinger’s equation)- time dependent
Fundamental equation of Quantum Mechanics
(like second law motion of Newtonian mechanics F=ma)
Is a wave equation in the variable
For standing wave equation in classical
y = A cos ( t kx ) 1
Let us consider the wave equivalent of a Free Particle in a straight path at
constant speed
This wave is described by general solution
y = A cos ( t kx ) i A sin ( t kx ) 2
(If undamped, monochromatic harmonic wave in + x direction)
2 can be written in the for
y Ae i (t - kx )
Only real part of (2) has significance in the case of waves in a stretched string.
‘y’ means displacement , imaginary is discarded as irrelevant.
In quantum mechanics the wave function ‘’ corresponds to the wave
variable ‘y’ of wave motion in general.
However, - is not measureable quantity and may therefore be complex
Ae i (t - kx )
It convenient to change and k in terms of total energy ‘E’ and momentum
‘p’ of the particle being described by ‘’
i
Et px
Ae
-3
Since
E= h = 2 * h/ 2 = ħ
E= ħ =E/ ħ
=h/p p =h/ = = (h/ 2)* (2 / )
P= ħk k = P/ ħ
(3) describes the wave equivalent of an unrestricted particles
of total energy ‘E’ and momentum ‘p’ moving in + x direction
Wave function ‘’ given by (3) is correct only for free moving
particle
However motion of particle with various restriction are
interested
e.g. Electron bound to an atom by electric filed of nucleus
A particle can have as a wave only under motion,
So the total energy E of the particle is sum of K.E and its potential energy U,
Where U is in a function of position ‘x’ and time ‘t’
1 2
E mv U ( x, t )
2
2 2
1mv
E U
2 m
p2
E U -(4)
2m
multiplying both side of eq. 4 with wave function
p2
E U -(5)
2m
Aim to obtain the fundamental differential equation for ‘’
- solve for ‘’ in a specific situation
Differentiating eq. 3 for ‘’ twice w.r.t ‘x’
ip i Et px ip
Ae
x
i p
2 2 2
i
Et px p 2
Ae
2
x 2
2
2
p
2 2
x 2 ------- 6
differenti ating eq.3 once w.r.t. ' t'
iE i Et px iE
Ae
t
E E i
i t t ------7
Substitute ‘E’ and p2
2 2 -(8)
i U
t 2m x 2
in three dimensions the time - dependent form of schrodinger eq.
2 2 2 2
i 2 2 2 U
t 2m x y z
2 2
i U
t 2m -(9)
E H
E i energy operator
t
2 2
H U Hamiltonian operator
2m
Schrodinger’s time independent equation
Let us consider a system of stationary wave associated a moving particle.
Let be the wave function of particle along x.
For simplicity we take 1 dimension Cartesian coordinate
i
Et px
then
Ae
x ,t
----- 3
ip
x
Removing time component
Ae x
----- 4
Differentiating eq. 4 w.r.t. x
x ip i
px ip
Ae x
x
2 x i 2 p 2 i
px p 2
Ae
2 x
x 2
2
2
x
p x
2 2
-(5)
x 2
p2
E U
2m
multiplying both side of eq. 4 with wave function x
p2
E x x U x
2m
-(6)
1 2 2 x
E x U x
2
2m x
2 2 x
E x U x
2m x 2
2 2 x
E U x
2m x 2
2m 2 x
E U x 2
2
x
2 x 2m
2 E U x
x 2
if in 3 dimention
2 r 2 r 2 r 2m
2 E U r
x 2
y 2
z 2
2m
r 2 E U r
2
laplacian operator
therefore
2m
r 2 E U r 0
2
Schrodinger equation obtained here is for wave function of
a freely moving particle
Then how far it applies to general case of particles subject
To arbitrary forces
Postulate Schrodinger eq. , solve it for a variety of physical
situation , compare the results of cal. And exp.
Both agree -> postulate is valid
Not agree-> postulate must be discarded and some other
approaches have to be explored
Schrodinger’s eq. cannot be derived from other basic principles
Of physics ; it is a basic principle in itself.
Remarkably accurate in predicting the results of exp.
Used only for non-relativistic problem
Elaborate formulation needed for relativistic
newton’s second law F=ma
Application of Schrodinger’s eq.
Particle in a Box or Infinite potential well
To solve Schrödinger eq. elaborate mathematics is needed
Simplest quantum mechanical problem
- particle trapped in a box with infinitely hard wall
Let us consider
- motion of a particle
along x – direction
within the region x= 0 and x= L
rigid walls of infinite height
- particle does not loss energy when it collides on walls
- potential energy is constant V(x) = 0 ; 0 < x < L
- potential energy is infinite V(x) = at x=0 and x = L ( 0xL)
Particle cannot have infinite energy so, it can not exist outside the box.
- rectangular potential box or potential well
of infinite depth and width L
Our task is to find what is with in the box
Height -
U(x)= U(x) = 0 U(x) =
x=0 x=L
Time independent Schrodinger ‘s equation for free particle
2 2m
2 E U 0
x 2
we have taken U(x) 0
2 2m
2 E 0
x 2
d 2
2
k 2
0 Total derivative is the same as partial
dx Derivative becs, is the function only
Of x
2m
where k 2 E
2
( x) A sin kx B cos kx
A and B are constants to be determined from boundary conditions
At x = 0, =0
0 = A sin k 0.0 + B cos k 0.0
0 = B -> (x) = A sin kx
And At x = L then =0 => 0 = A sin kL
A = 0 is meaning less, ie it means that no wave
kL = n ; where n = 1,2,3…..
k = n / L
Ö(2mE/ ħ2 ) = n / L
Energy of particle can not be any arbitrary values,
It can have only certain discrete values
2m n 2 2
2
En 2
L
n 2 2 2
En 2
where n 1,2,3.... ; are energy eigen valu es
2mL
N=0 is excluded since E0=0 then become ‘Zero’ which not
permissible physically and quantum mechanically
It s energy is quantized.
Wave function of particle in a box whose energy En with B=0
2mEn
( x) A sin x
n
( x) A sin x
L
For each n, is a finite, single valued function of ‘x’
n and dn/dx are continuous
Integral of | n |2 for over all space is finite.
To normalize we have to assign the value of A
( x) 2 dx 1
L
0
( x) 2 dx 1
n
L
A sin
2
x dx 1
2
0 L
A n
2 L L
dx cos 2 x dx 1 ; from trignamet ry;
2 0 0 L
2 L
A L 2n 1
x sin x 1 sin (1 - cos2 )
2
2 2 n L 0 2
2
A 2
L 1 A
2 L
The normalized wave function of the particle
2 n
n sin x n 1,2,3....
L L
0.4 0.4
0.2 0.2
0.0 4 |4|2 0.0
-0.2 -0.2
-0.4 -0.4
0.4 0.4
0.2 0.2
0.0
-0.2 3 |3|2 0.0
-0.2
-0.4 -0.4
0.4 0.4
0.2 0.2
0.0 0.0
-0.2 2 |2|2 -0.2
-0.4 -0.4
0.4 0.4
0.2 0.2
0.0 1 |1|2 0.0
-0.2 -0.2
-0.4 -0.4
0 2 4 6 8 10 0 2 4 6 8 10
A A
At particular place in the box the probability of the
particle Being present may
Vary for different quantum number
For instance |1|2 has its max. at L/2 (middle of box)
For instance | 2|2 has its 0 . at L/2 (middle of box)
Classical mechanic suggest the same probability for
the Particle being anywhere in the box
The wave function resemble the stretched string fixed
both ends
-same form of equation
Find the probability that a particle trapped in the box L wide can be
Found between 0.45L and 0.55L for the ground and first exited states
x2
Px1, x 2
x1
( x) 2 dx
2 n
x2
2
sin x dx
L x1 L
x2
x 1 2 n
sin x
L 2n L x1
n= 1 P x1,x2 =0.198 then 19.8 percent
n= 2 P x1,x2 =0.0065 then 0.65 percent
A eikx + B e-ikx
A coskx + iA sinkx +B coskx – iB sinkx
(A+B) coskx + i(A-B)sinkx
C1 coskx+C2 sinkx
