Lecture 2: Schrodinger equation
and wave functions
The Schrodinger equation and wave functions operators
The quantum mechanical systems views dynamics of microscopic system
as a particle being spread through space like a wave. There are regions
where it’s more likely to be found than others.
The distribution is specified by a statefunction, , called ‘wavefunction’ as
opposed to the trajectory. , a blurred version of the trajectory.
contains all the information we want to know about the system.
Schrodinger equation is the proposed equation for calculating Ψ of any
system
Schrodinger eqn for a free particle moving in one dimension in a constant (zero)
potential
2 d 2
2
V E
2m dx
PE of the particle
h-bar or h-cross is the modified Plank’s constant = h/2
The general solution of this Schrodinger equation is
(x) = Aexpikx + Bexp-ikx and energies
2k 2
E
2m
(x) = c1eikx + c2e-ikx for a single particle of mass m
moving in 1D with energy E and PE zero
(Invoke Eulers formula: eix = cosx isinx)
(x) = c1(coskx + isinkx) + c2(coskx – isinkx)
= (c1 + c2) coskx + (c1 – c2) isinkx
Let (c1 + c2) be d1 and (c1 – c2 ) be d2
Then, at x = 0 (0) = d1cos0 + d2sin0 = d1 = 0
At x = l (having d1 = 0) (l) = d2sinkl = 0
kl = n,
n
k n = 0, ±1, ±2, ...
l
The particle’s energy is entirely kinetic (since v = 0)
p2
p 2 k 2 2
E , p k
2m 2m 2m
2
Sinkx, so too asinkx is a wave of wavelength,
k
2
k
2
h h
Then
p The de Broglie’s relation which is
2 experimentally found but has been proved using
the Schrodinger equation.
Boundary conditions
Schrodinger eqn is a differential equation hence, common to have infinite
number of solutions.
If sinx is a soln then asinbx is also a solution with a and b being arbitrary
constants.
Acceptable soln satisfies certain constraints called boundary conditions.
When the Schrodinger equation is solved subject to the boundary conditions that
the solution must satisfy we find that the energy of the system is quantized.
Quantization is an automatic feature of a single equation, the Schrodinger eqn,
which is applicable to all systems
Interpretation of the wavefunction
Born interpretation: the probability of finding a particle in a small (strictly
infenitesmall region of space of volume V is proportional to 2V, where
is the value of the wavefunction.
2 is a probability density. The larger the 2 the higher the probability of
finding the particle. We were able to predict precisely that a particle will be
at a given point on its path at a given instant in classical physics.
Example. The of an electron in the lowest energy state of a hydrogen
atom is proportional to:
r
ao
e
with ao = 52.9 pm and r the distance from the nucleus. Calculate the
relative probabilities of finding the electron inside a small volume located at
(a) the nucleus, (b) a distance ao from the nucleus.
Solution
Probability 2 d 2 1.0 pm
volum e
At the nucleus r = 0 and so 2 = 1.0 and probability 1.0 pm3.
(b) 2 = e-2 = 0.14. Probability 0.14 x 1.0 pm3.
Normalization
Have to find a factor so that the proportionality of the Born interpretation
becomes an equality.
If is a solution so too is N where N is a constant
Probability of a particle being in region dx is equal to N X Ndx
The total probability is 1 1
1 2
N
Hence
N 2 dx 1 dx
This procedure is called normalization of the wavefunction.
Shall assume that is already normalized in the subsequent discussions.
Example,
A certain wavefunction is zero everywhere except between x = 0 and x = L,
where it has the constant value A. Normalize the wavefunction.
Solution:
Find the normalization constant, N
The normalized wavefunction is = NA
1
1 2
N
A Adx
1
1 2 1
N 2 N
1
A L
AL2
1A 1
Normalized N 1
A 1
2 2
AL L
General Schrodinger equation
For three dimensional problems
2 2
( x, y , z ) r
V ( x, y, z ) E
2m
2
2
2
Where 2 2 2
2
x y z
2m
Also encountered in the form: 2 E V r 0
2
For systems with spherical symmetry it is more appropriate to regard as a
function of the polar coordinates , r, , .
In general case, the Schrodinger equation is written H = E.
H is the Halmitonian operator for the system;
2 2
V r
H
2m
Operators and eigenvalues
H = E.
with H 2
d 2
2
V
2m dx
H is an operator: operates on the function i.e it takes 2nd derivative of and
(after multiplication by - 2) adds to the results of multiplying by V.
2m
H is called the Halmitonian operator
(operator)(function) = (numerical factor)(same function).
The numerical factor is called the eigenvalue of the operator i.e the eigenvalue
above is the energy. The function is called the eigenfunction corresponding
to that eigenvalue.
Examples:
Show that eax is an eigenfunction of the operator d/dx and find the
corresponding eigenvalue.
Answer: (operator)(function) = deax/dx = aeax = (numerical factor)(function)
ex 2
Show that e is not an eigenfunction of d/dx
Uncertainty principle
Proposed by Werner in 1927
It is impossible to specify simultaneously with arbitrary precision both the
momentum and the position of a particle.
Quantitatively
px
2
p = uncertainty in linear momentum, x = uncertainty in position.
The more closely the location of a particle is specified the greater the
uncertainty in momentum parallel to that coordinate and vice versa.
Classical mechanics could specify precisely.
Example: The speed of a certain projectile of mass 1.0 g is known to within
1.0x10-6 ms-1. What is the minimum uncertainty in its position along the line
of flight?
