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Lec 3
Lec 3
Lecture 3
NC State University
Derivation of the Schrdinger Equation
The Schrdinger equation is a wave equation.
Just as you might imagine the solution of such an equation
in free space is a wave. Mathematically we can express a
wave as a sine or cosine function. These functions are
oscillating functions. We will derive the wave equation in
free space starting with one of its solutions: sin(x).
d
sin(x) = cos(x)
dx
The derivative of cos(x)
d
cos(x) = -sin(x)
dx
The second derivative of sin(x)
d d
sin(x) = -sin(x)
dx dx
The second derivative of sin(x)
d2
sin(x) = -sin(x)
dx2
Sin(x) is an eigenfunction
d2
If we define - as an operator G then we have:
dx2
d2
- sin(x) = sin(x)
dx2
which can be written as:
G sin(x) = sin(x)
d
- sin(kx) = -k cos(kx)
dx
d2
- sin(kx) = k2sin(kx)
dx2
Here we call the value k2 the eigenvalue.
Sin(kx) is an eigenfunction
of the Schrdinger equation
The example we are using here can easily be expressed
as the Schrodinger equation for wave in space. We only
have to add a constant.
-h2 d2 -h2k2
- sin(kx) = sin(kx)
2m dx2 2m
In this equation -h is Plancks constant divided by 2 and
m is the mass of the particle that is traveling through space.
The eigenfunction is still sin(kx), but the eigenvalue in
this equation is actually the energy.
The Schrdinger equation
Based on these considerations we can write a compact
form for the Schrdinger equation.
H = E
-h2 d2
H=- Energy operator, Hamiltonian
2m dx2
-h2k2
E= Energy eigenvalue, Energy
2m
Wavefunction
= sin(kx)
The momentum
The momentum is related to the kinetic energy. Classically
The kinetic energy is: 1 2
E = mv
2
The momentum is:
p = mv
0 Allowed Region L
The solution to the Schrdinger
equation with boundary conditions
Suppose a particle is confined to a space of length L.
On either side there is a potential that is infinitely large.
The particle has zero probability of being found at the
boundary or outside the boundary.
0 Allowed Region L
The solution to the Schrdinger
equation with boundary conditions
The boundary condition is that the wave function will
be zero at x = 0 and at x = L.
(0) = Asin(k0) + Bcos(k0) = 0
From this condition we see that B must be zero.
This condition does not specify A or k.
The second condition is:
A sin nx sin nx
L L 2 L 2
2 2 2
1= dx = dx = A dx
0 0 L 0 L
The solution to the integral is available on the
downloadable MAPLE worksheet. The solution is just L/2.
Thus, we have:
1=A L ,A = 2 ,A= 2
2 2
2 L L
As you can see the so-called normalization constant has
been determined.
Normalization
What is the normalization constant for the wave function
exp(-ax) over the range from 0 to infinity?
A. a
B. 2a
C. a
D. 2a
Normalization
What is the normalization constant for the wave function
exp(-ax) over the range from 0 to infinity?
A. a
B. 2a
C. a
D. 2a
L
2
1= 2dx = A 2exp ax dx = A 2 exp 2ax dx
0 0 0
= A 1 , A = 2a
2
2a
The appearance of the wave functions
The appearance of the wave functions
Note that the wave functions have
nodes (i.e. the locations where they
cross zero). The number of nodes is
n-1 where n is the quantum number
for the wave function. The appearance
of nodes is a general feature of
solutions of the wave equation in bound states. By bound
states we mean states that are in a potential such as the
particle trapped in a box with infinite potential walls. We
will see nodes in the vibrational and rotational wave functions
and in the solutions to the hydrogen atom (and all atoms).
Note that the wave functions are orthogonal to one another.
This means that the integrated product of any two of these
functions is zero.
The energy levels
The energy levels are:
2 2
E= n h
2
8mL
The probability of finding the
particle in a given region of space
Using the normalized wave function
x = 2 sin nx
L L
one can calculate the probability of finding the particle
in any region of space. Since the wave function is
normalized, the probability P is a number between 0 and 1.
For example: What is the probability that the particle is
between 0.2L and 0.4L. This is found by integrating over
this region using the normalized wave function (see MAPLE
worksheet). 0.4L
nx
0.4L
P = x dx =
2 2 sin
2
dx 0.25
0.2L L 0.2L L
The appearance of the probability 2
The probability of finding the
particle in a given region of space
Using the normalized wave function
x = 2 sin nx
L L
one can calculate the probability of finding the particle
in any region of space. Since the wave function is
normalized, the probability P is a number between 0 and 1.
For example: What is the probability that the particle is
between 0.2L and 0.4L. This is found by integrating over
this region using the normalized wave function (see MAPLE
worksheet). 0.4L
nx
0.4L
P = x dx =
2 2 sin
2
dx 0.25
0.2L L 0.2L L
Solutions of the Schrodinger equation
are orthogonal
If the wavefunctions have different quantum numbers
Then their overlap is zero. We can call the integral
Of the product of two wavefunctions an overlap. We write:
L
mndx = mn
0
sin mx sin nx dx = mn
L
2
L 0 L L
Postulates of quantum mechanics
are assumptions found to be
consistent with observation
The first postulate states that the state of a
system can be represented by a wavefunction
(q1, q2,.. q3n, t). The qi are coordinates of
the particles in the system and t is time.
P(a) = d
0
Assumptions for the Born interpretation
1. * is real ( is Hermitian).
2. The wavefunction is normalized.
3. We integrate over all relevant space.
Normalization is needed so that
probabilities are meaningful
Normalization means that the integral of the
square of the wavefunction (probability density)
over all space is equal to one.
d = 1
all space
The significance of this equation is that the
probability of finding the particle somewhere
in the universe is one.
Postulate 3. Every physical
observable is associated with a
linear Hermitian operator
Observables are energy, momentum, position,
dipole moment, etc.
operator P observable P
The fact that the operator is Hermitian ensures
that the observable will be real.
Postulate 4. The average
value of a physical property
can be calculated by
Pd
P =
d
Normalization
Postulate 4. The calculation of
a physical observable can be
written as an eigenvalue
equation
P = P
This is an operator equation that returns the
same wavefunction multiplied by the constant P.
P is an eigenvalue. An eigenvalue is a number.
The form of the operators is
Position q q
Momentum P ih
q
Time t t
Energy H ih
t
Postulate 5. It is impossible to specify
with arbitrary precision both the
position and momentum of a particle
This postulate is known as the Heisenberg
Uncertainty Principle. It applies not only to
the pair of variables position and momentum,
but also to energy and time or any two conjugate
variables.
Conjugate variables are Fourier transforms of
one another.
Conjugate variables do not commute.
Commutator in quantum mechanics
A commutator is an operation that compares the
order of operation for two operators:
[ p,x] = px x p
Since the momentum, p involves a derivative,
the order of application affects the result. The way
to see the result of the commutator is to apply it to
a test function f(x).
pxf(x) = -ih(f(x) + xf(x)) while xpf(x)= -ihxf(x).
Therefore [p,x] = - ih.
We say that position and momentum do not
Commute.