E. F.

Schubert
37

Erwin Schrdinger (18871961)
Established quantum mechanical wave equation


6

The Schrdinger equation


6.1 The time-dependent Schrdinger equation
The Schrdinger equation is the key equation of quantum mechanics (Schrdinger 1925, 1926a,
1926b). This second order, partial differential equation determines the spatial shape and the
temporal evolvement of a wave function in a given potential and for given boundary conditions.
The one-dimensional Schrdinger equation is used when the particle of interest is confined to
one spatial dimension, for example the x axis. Here, we restrict our considerations to such one-
dimensional cases. Due to the one-dimensional nature of many semiconductor heterostructures,
the one-dimensional Schrdinger equation is sufficient for most applications. To derive the one-
dimensional Schrdinger equation, we start with the total energy equation, i. e. the sum of
kinetic and potential energy

total
2
) (
2
E x U
m
p
= + . (6.1)
Substitution of the dynamical variables by their quantum mechanical operators which act on the
wave function (x, t) yields the one-dimensional time-dependent Schrdinger equation
) , (
i
) , ( ) ( ) , (
2
2
2 2
t x
t
t x x U t x
x
m

= +

h h
(6.2)
The left side of this equation can be rewritten by using the hamilton or total energy operator
) (
2
2
2 2
x U
x
m
H +

=
h
. (6.3)

E. F. Schubert
38
Using the notation of the Hamilton operator, the time-dependent Schrdinger equation can be
written as
) , (
i
) , ( t x
t
t x H

=
h
(6.4)
Since the Schrdinger equation is a partial differential equation, the product method can be used
to separate the equation into a spatial and a temporal part
) ( f ) ( ) , ( t x t x = (6.5)
where (x) depends only on x and f(t) depends only on t. Insertion of Eq. (6.5) into the
Schrdinger equation yields
) ( f
d
d
) ( f
i
) (
) (
1
t
t t
x H
x
h
=

. (6.6)
The left side of this equation depends on x only, while the right side depends only on t. Because
x and t are completely independent variables, the equation can be true, only if both sides are
constant.
. const ) ( f
d
d
) ( f
i
= t
t t
h
(6.7)
Tentatively this constant is designated as const. = E where the meaning of E will become evident
below. Integration of Eq. (6.7) yields

h / i
e ) ( f
Et
t

= . (6.8)
Insertion of this result into Eq. (6.5) yields the time-dependent wave function

h / i
e ) ( ) , (
Et
x t x

= (6.9)
If E is real, then the wave function has an amplitude (x) and a phase exp(iEt

/

). The
amplitude and phase representation is convenient for many applications. To find the physical
meaning of the real quantity E, we calculate the expectation value of the total energy using the
wave function obtained from the product method.
E x x x E x t x
t
t x E
Et Et
= =

d ) ( ) ( e e d ) ( f ) (
i
) ( f ) (
*
i i
* *
total
h h
h
.
(6.10)
Because the wave function is normalized, that is (x)(x) = 1, the constant designated as E is
the expectation value of the total energy.


E. F. Schubert
39
6.2 The time-independent Schrdinger equation
The time-independent Schrdinger equation is obtained by inserting the wave function obtained
from the product method, Eq. (6.9) into the time-dependent Schrdinger equation (see Eq. 6.2).
One obtains
) ( ) ( ) ( ) (
d
d
2
2
2 2
x E x x U x
x
m
= +
h
(6.11)
which is the time-independent Schrdinger equation. Using the hamiltonian operator, one
obtains
) ( ) ( x E x H = . (6.12)
Since H is an operator and E is a real number, the Schrdinger equation has the form of an
eigenvalue equation. The eigenfunctions
n
(x) and the eigenvalues E
n
are found by solving the
Schrdinger equation.
The eigenvalues of the Schrdinger equation, E
n
, are discrete, that is only certain energy
values are allowed, all other energies are disallowed or forbidden. The energy eigenvalues are
also called eigenenergies or eigenstate energies. The lowest eigenstate energy is the ground
state energy. All higher energies are called of excited state energies.
The solution of the Schrdinger equation and the eigenstate energies and wave functions of a
physical system are of great importance, because the knowledge of
n
(x) and E
n
implies the
knowledge of all relevant physical parameters. It is the purpose of the next sections to get
familiar with the properties of the Schrdinger equation and its solutions.

6.3 The superposition principle
Mathematically speaking the Schrdinger equation is a linear, second order, partial differential
equation. Any linear differential equation allows for the superposition of its solutions. That is, if

n
and
m
are solutions of the Schrdinger equation, then any linear combination of
n
and
m

are solutions as well. That is, a new solution of Schrdingers equation is given by
) , ( ) , ( ) , ( t x B t x A t x
m n
+ = (6.13)
where, A and B are real constants. For practical physical problems, the Schrdinger equation has
always more than one solution. Thus, the superposition principle can be applied to all physical
problems in order to obtain a new solution. The new solution (x, t) must be normalized as well,
that is | = 1.

6.4 The orthogonality of eigenfunctions
If two eigenfunctions
n
=
n
(x) and
m
=
m
(x) are solutions of the Schrdinger equation and
the two eigenfunctions belong to different energies E
n
and E
m
(so that E
n
E
m
), then the
eigenfunctions are orthogonal:
0 =
m n
. (6.14)
This equation can be proven by starting with the Schrdinger equation for
n
(x) and the complex
conjugate equation for
m
, that is

E. F. Schubert
40

n n n n
E U
x
m
= +
2
2 2
d
d
2
h
(6.15)
and

* * *
2
2 2
d
d
2
m m m m
E U
x
m
= +
h
. (6.16)
Multiplication of Eq. (6.15) with
m
* and of Eq. (6.16) with
n
and subtraction of the two
resulting equations yields
( ) .
d
d
d
d
2
*
2
2
* *
2
2 2
m n m n n m m n
E E
x x
m
=

h
(6.17)
Using the identity


n m m n n m m n
x x
x x x
=

2
2
* *
2
2
* *
d
d
d
d
d
d
d
d
d
d
(6.18)
and integrating over x yields
( ) . d d
d
d
d
d
d
d
2
* * *
2

x E E x
x x x m
n m m n n m m n
h
(6.19)
The integral on the left side of the equation simplifies to
+

n m m n n m m n
x x
x
x x x d
d
d
d
d
d
d
d
d
d
d
* * * *
(6.20)
This expression is zero due to the normalization condition which requires that (x ) = 0.
Hence, we obtain the following condition for the eigenvalues and eigenfunctions
( ) 0 d
2
*
2
=



x E E
m
n m m n
h
. (6.21)
Because E
n
E
m
, this equation can be true, only if
0 d
*
=

x
n m
(m n) (6.22)
which concludes the proof that
m
and
n
are orthogonal. Together with the normalization
condition, one obtains

E. F. Schubert
41

. ) ( 1
) ( 0
d
*
n m
n m
x
n m
(6.23)
This result can be also written as

mn n m
= (6.24)
where
mn
is the Kronecker delta which is defined as

=
. ) ( 1
) ( 0
n m
n m
mn
(6.25)

6.5 The complete set of eigenfunctions
Consider a practical physical problem given by the potential energy U(x, y, z). Assume further
that at least one solution of the Schrdinger equation exists for the potential energy U(x, y, z).
Generally, the number of solutions is large but finite. The solutions of the Schrdinger equation
are designated a set of solutions. Such a set of solutions is a complete set of solutions, if it
contains all possible solutions. If, in addition, each solution of the set is normalized and if the
solutions are orthogonal, then the solutions are called an orthogonal, normal, complete set or,
abbreviated, a orthonormal complete set of solutions. Such an orthonormal complete set of
solutions provides any solution of a physical problem by superposition (linear combination) of
the individual solutions.