SCHRODINGER WAVE MECHANICS

Until 1925, all attempts to deal with atomic and molecular structural
problems were based on classical mechanics, in which the structural units of the
atom were treated as particles with determined momenta and positions upon which
were superimposed postulated quantized conditions such as those of Bohr. In 1925-
1926, Werner Heisenberg and Erwin Schrdinger independently propped a new
quantum or wave mechanics which takes cognizance of the wave and particle
duality of matter and which deals with atomic and molecular scale problems in a
totally different manner. Erwin Schrdinger was an Austrian theoretical physicist who
achieved fame for his contributions to quantum mechanics. Schrdinger equation, which he
formulated in 1926 to describe the quantum state of a system, is his most enduring achievement
at a more technical level. Also, he produced the papers that gave the foundations
of quantum wave mechanics. In those papers he described his partial differential
equation that is the basic equation of quantum mechanics and bears the same
relation to the mechanics of the atom as Newtons equations of motion bear to

planetary astronomy.

Adopting a proposal made by Louis de Broglie in 1924 that particles of matter

have a dual nature and in some situations act like waves, Schrdinger introduced a
theory describing the behavior of such a system by a wave equation that is now
known as the Schrdinger equation. The solutions to Schrdingers equation, unlike
the solutions to Newtons equations, are wave functions that can only be related to
the probable occurrence of physical events. The definite and readily visualized
sequence of events of the planetary orbits of Newton is, in quantum mechanics,
replaced by the more abstract notion of probability.

The basis for handling all problems by wave mechanics is the Schrodinger
equation. This equation cannot be derived from the first principles or basic
postulates. Rather, it is arrived at in a manner to be described below, and the
assumption is then made that this equation is valid for the treatment of all types of
problems which involve atomic and molecular behavior.

Consider a system, such a string, vibrating with a frequency v and producing

a wave traveling in the x direction with a velocity ux and amplitude (height of wave)
. For such a system classical mechanics tells us that (Eq. 25)

2 1 2
=
x 2 u 2x t 2

Where t is the time necessary for the wave to reach a position x. The solution of this
equation can be obtained in the form (Eq. 26)

=f 1 ( x ) f 2 (t )
Where f1(x) is a function only of x and f2(t) can be written as (Eq. 27)

f 2 ( t )= A sin 2 vt

Where A is the maximum amplitude of the wave. Consequently (Eq. 28)

=f 1 ( x ) A sin 2 vt

If we differentiate =f 1 ( x ) f 2 (t ) with respect to x at constant t, we obtain (Eq. 29)

2
2 f 1 ( x)
2
=f 2 ( t ) 2
x x

Again a similar differentiation of =f 1 ( x ) A sin 2 vt with respect to t at constant x

gives (Eq. 30)

2
2
=4 2 v 2 f 1 ( x ) A sin 2 vt
t

2 2 2
2
=4 v f 1 ( x ) f 2 ( t )
t

And hence on substitution of Eq. (29) and Eq. (30) into Eq. (25) we get (Eq. 31)

2 f 1 ( x ) 4 2 v 2
= f 1(x)
x2 u2x

But wave length =ux/v. Making this substitution, (Eq. 31) becomes (Eq. 32)

2 2
f 1( x ) 4
2
= 2
f 1(x)
x

Equation (32) applies to a wave moving in the x direction only. If we consider a wave
moving in three dimensions, then f1(x) can be replaced by , where = (x,y,z),
and Eq.(32) is transformed to Eq.(33)

2 2 2 4 2
+ + = 2
x2 y 2 z 2

Or Eq. (34)

2
4
2 = 2

Where the symbol 2 (del squared) represents Eq. (35)

 2 2 2 2
= + +
x2 y 2 z 2

Again according to de Broglies hypothesis a wave of length can be considered to

be a particle of mass m moving with a velocity v, namely = h/mv . Substituting
the latter into Eq. (34), we obtain Eq. (36)

4 2 m2 v 2
2 =
h2

Finally, the total energy of the particle, E, is the sum of its potential energy, U, and
its kinetic energy Ek = (1/2) mv2. Consequently,

1
Ek = ( EU ) = m v 2
2

And

m v 2=2( EU )

Substitution of the latter expression to Eq. (36) thus yields Eq. (37)

8 2m (
2 + EU ) =0
h2

which is the Schrodingers wave equation, and the postulated basis of all quantum
mechanical behavior of matter.

TIME-INDEPENDENT SCHRODINGER EQUATION

2 d 2
+V ( x ) =E
2 mdx 2

Where:

V(x) = the potential energy of the particle at the point x

E = sum of potential and kinetic energies

= convenient modification of Plancks constant

h
= =1.05457 1034 Js
2

In general case, Schrodinger equation is written

=E

Where is the Hamiltonian operator for the system:

 2
2
= +V
2m

For the evolution of a system with time, it is necessary to solve the time-dependent
Schrodinger equation:

=i
t

Although the Schrodinger equation should be regarded as a postulate, like Newtons

equations of motion, it can be seen to be plausible by noting that it implies the de
Broglie relation for a freely moving particle in a region with constant potential
energy V:

d 2 2m
2
= 2 ( EV )
dx

General strategies for solving differential equations of this and other types that
occur frequently in physical chemistry, we note that a solution is:

=eikx

V
E 2

Where 2 m1 /2

k=

In quantum mechanics, a wave function that describes the spatial distribution of a

particle (a spatial wave function) is complex if the particle it describes has a net
i
motion. In the present case, we can use the relation e =cos +i sin to write

=cos kx +isin kx .

The real and imaginary parts of can be shown as

 Source: Atkins

and we see that the imaginary component lm ( )=sin kx is shifted in the direction

of the particles motion. That is both the real and imaginary parts of the
wavefunction are real, in the sense of being present, and we express as a
complex function simply to help the visualization of the motion of the particle the
wavefunction describes.

kx
sin 2
is a wave of wavelength = , as can be seen by comparing cos kx
kx k
cos

2 x /
with the standard form of a harmonic wave, ). The quantity EV is
cos

1 /2
2 m Ek
equal to the kinetic energy particle, Ek, so k =( 2
) , which implies that

k 2 2 p2
Ek = . Because Ek = , it follows that
2m 2m

p=k

Therefore, the linear momentum is related to the wavelength of the wavefunction

by
 2 h h
p= =
2

which is the de Broglie relation.