MOLECULAR

QUANTUM
MECHANICS,
FOURTH EDITION

Peter Atkins
Ronald Friedman

OXFORD UNIVERSITY PRESS



Total amplitude,
Time, t
Fig. 2.11 Because each wave in a
superposition oscillates with a
different frequency, the point of
constructive interference moves as
time increases.
V
2 d2
0Þ: H¼ þV
Potential energy, V (x )
Zone I
0 x
Fig. 2.12 The potential energy
of a barrier of finite height but
of semi-infinite extent.
2.9 AN INFINITELY THICK POTENTIAL WALL j 51
the region of constructive interference changes with time (Fig. 2.11). It should
not be hard to believe that the centre of the packet moves to the right, and
this is confirmed by a mathematical analysis of the motion (see Further
information 5). The classical motion of a projectile is captured by the motion
of the wavepacket, and once again we see how classical mechanics emerges
from quantum mechanics.
x
Penetration into and through barriers
A highly instructive extension of the results for free translational motion is
to the case where the potential energy of a particle rises sharply to a high,
constant value, perhaps to decline to zero again after a finite distance.
Classically we know what happens: if a particle approaches the barrier from
the left, then it will pass over it only if its initial energy is greater than the
potential energy it possesses when it is inside the barrier. If its energy is lower
than the height of the barrier, then the particle is reflected. To see what
quantum mechanics predicts, we shall consider three types of barrier of
increasing difficulty.
2.9 An infinitely thick potential wall
The Schrödinger equation for the problem falls apart into two equations,
one for each zone in Fig. 2.12. The hamiltonians for the two zones are

2 d2
h
Zone I ðx < 0Þ: H¼
2m dx2
ð2:14Þ
h
Zone II ðx
2m dx2
The corresponding equations are free-particle Schrödinger equations, except
for the replacement of E by E  V in Zone II. Therefore, the general solutions
can be written down by referring to eqn 2.5:
Zone II Zone I: c ¼ Aeikx þ Beikx h ¼ f2mEg1=2
k

ð2:15Þ
h ¼ f2mðE  VÞg1=2
0 0
Zone II: c ¼ A0 eik x þ B0 eik x k0

We shall concentrate on the case when E < V, so that classically the particle
cannot be found at x > 0 (inside the wall). The condition E < V implies that k 0
is imaginary; so we shall write k 0 ¼ ik, where k (kappa) is real. It then follows
that
Zone II: c ¼ A0 ekx þ B0 ekx h ¼ f2mðV  EÞg1=2
k
ð2:16Þ
This wavefunction is a mixture of decaying and increasing exponentials: we
see that a wavefunction does not oscillate when E < V.
Because the barrier is infinitely wide, the increasing exponential must be
ruled out because it leads to an infinite amplitude. Therefore, inside a barrier
like that shown in Fig. 2.12, the wavefunction must be simply an exponen-
tially decaying function, ekx. One important point about this conclusion is
52 j 2 LINEAR MOTION AND THE HARMONIC OSCILLATOR
V particular, the potential energy, V(x), has the form:
Potential energy, V (x )
LÞ: VðxÞ ¼ 0
Zone I
Fig. 2.13 The potential energy
of a finite barrier. Particles incident
from one side may be found on the
opposite side of the barrier.
According to classical mechanics,
that is possible only if E is not less
than V. According to quantum
mechanics, however, barrier
penetration may occur whatever
the energy.
that, because the wavefunction is non-zero inside the barrier, the particle may
be found inside a classically forbidden region, the effect called penetration.
The rapidity with which the wavefunction decays to zero is determined by the
value of k, for the amplitude of the wavefunction decreases to 1/e of its value
at the edge of the barrier in a distance 1/k, which is called the penetration
depth. The penetration depth decreases with increasing mass of the particle
and the height of the barrier above the energy of the incident particle (the
value of V  E). Macroscopic particles have such large masses that their
penetration depth is almost zero whatever the height of the barrier, and for
all practical purposes they are not found in classically forbidden regions.
An electron or a proton, on the other hand, may penetrate into a forbidden
zone to an appreciable extent. For example, an electron that has been
accelerated through a potential difference of 1.0 V, and which has acquired
a kinetic energy of 1.0 eV, incident on a potential barrier equivalent to 2.0 eV,
will have a wavefunction that decays to 1/e of its initial amplitude after
0.20 nm, which is comparable to the diameter of one atom. Hence, pene-
tration can have very important effects on processes at surfaces, such as
electrodes, and for all events on an atomic scale.
2.10 A barrier of finite width
We now consider the case of a barrier of a finite width (Fig. 2.13). In
Zone I ðx < 0Þ: VðxÞ ¼ 0
Zone II ð0  x < LÞ: VðxÞ ¼ V ð2:17Þ
Zone III ðx
The general solutions of the time-independent Schrödinger equation can be
Zone II Zone III written down immediately:
Zone I: c ¼ Aeikx þ Beikx h ¼ f2mEg1=2
k

0 L x
h ¼ f2mðE  VÞg1=2
0 0
Zone II: c ¼ A0 eik x þ B0 eik x 0
k
ð2:18Þ
Zone III: c ¼ A00 eikx þ B00 eikx h ¼ f2mEg1=2
k

In scattering problems, of which this is a simple example, it is common to
distinguish between ‘incoming’ and ‘outgoing’ waves. An incoming wave is a
contribution to the total wavefunction with a component of linear momen-
tum towards the target (from any direction). An outgoing wave is a con-
tribution with a component of linear momentum away from the target. Each
contribution corresponds to a flux of particles either towards or away from
the target. In the problem we are currently considering, in Zone I A is the
coefficient of the incoming wave and B the coefficient of the outgoing wave.
In Zone III, A00 is the coefficient of the outgoing wave and B00 the coefficient of
the incoming wave.
In this section we first consider solutions for E < V. Classically, the particle
does not have enough energy to overcome the potential barrier. Therefore,
for a particle incident from the left, the probability is exactly zero that it will be
found on the right of the barrier (x > L). Quantum mechanically, however,
the particle can be found on the right of the barrier even though E < V.
 2.10 A BARRIER OF FINITE WIDTH j 53

In Zone II, the wavefunction has the form given in eqn 2.16. We need to note
that the increasing exponential function in the wavefunction in this zone will
not rise to infinity before the potential has fallen to zero again and oscillations
resume. Therefore, the coefficient B 0 will not be zero. The values of the
coefficients are established by using the acceptability criteria for wavefunc-
tions set out at the beginning of this chapter, and in particular the requirement
that they and their slopes must be continuous. The continuity condition lets us
match the wavefunction at the points where the zones meet, and therefore to
find conditions for the coefficients. For example, the continuity of the
amplitude at x ¼ 0 and at x ¼ L leads to the two conditions
At x ¼ 0: A þ B ¼ A0 þ B0
ð2:19Þ
At x ¼ L: A0 ekL þ B0 ekL ¼ A00 eikL þ B00 eikL
Similarly, the continuity of slopes at the same two points leads to the two
conditions
At x ¼ 0: ikA  ikB ¼ kA0 þ kB0
ð2:20Þ
At x ¼ L: kA0 ekL þ kB0 ekL ¼ ikA00 eikL  ikB00 eikL
These four equations give four conditions for finding six unknowns.
The remaining conditions include a normalization requirement (one more
condition) and a statement about the initial state of the particle (such as the
fact that it approaches the barrier from the left).
Consider the case where the particles are prepared in Zone I with a linear
momentum that carries them to the right. It then follows that the coefficient
B00 ¼ 0, because the exponential function it multiplies corresponds to particles
with linear momentum towards the left on the right-hand side of the barrier,
and there can be no such particles. That is, there is no incoming wave, no
inward flux of particles, in Zone III. There may be particles travelling to the
left on the left of the barrier because reflection can take place at the barrier.
We can therefore identify the coefficient B as determining (via jBj2) the flux
density of particles reflected from the barrier in Zone I. The reflection prob-
ability, R, is the ratio of the reflected flux density to the incident flux density,
so from the results of Illustration 2.1 we can write (disregarding signs):

h=mÞjBj2
ðk
jBj2
R¼ ¼ ð2:21aÞ
h=mÞjAj2
ðk
jAj2
Similarly, the coefficient A00 , the coefficient of the outgoing wave in Zone III,
determines (via jA00 j2) the flux of particles streaming away from the barrier on
the right. The transmission probability, T, is the ratio of the transmitted flux
density to the incident flux density, and is given by
jA00 j2
T¼ ð2:21bÞ
jAj2
The complete calculation of T involves only elementary manipulations of the
relations given above, and the result is
1
T¼ 2
R¼1T ð2:22Þ
1þ ðekL  ekL Þ =f16ðE=VÞð1  E=VÞg
54 j 2 LINEAR MOTION AND THE HARMONIC OSCILLATOR

0.5 with k ¼ {2mV(1  E/V)}1/2/
h. Because we have been considering energies

E < V, T represents the probability that a particle incident on one side of
the barrier will penetrate the barrier and emerge on the opposite side. That is,
Transmission probability, T

0.4
T is the probability of tunnelling, non-classical penetration, through the
barrier (Fig. 2.14).
2 We now deal with energies E > V. Classically, the particle now has suffi-
0.3
cient energy to overcome the potential barrier. A particle incident from the
left would have unit probability of being found on the right of the barrier.
0.2 3 Once again, though, quantum mechanics gives a different result. To deter-
mine the expressions for T and R we could proceed as we did above for
4
0.1 energies E < V, write down four relations for the six coefficients, and then
6
8 manipulate them. However, it is considerably easier to take the expression for
10
T given above and replace k by k 0 /i ¼ ik 0 . This procedure gives
0
0 0.2 0.4 0.6 0.8 1.0 1
E/V
T¼ R¼1T ð2:23Þ
1 þ ðsin2 ðk0 LÞÞ=f4ðE=VÞðE=V  1Þg
Fig. 2.14 The tunnelling probability hk0 ¼ f2mVðE=V  1Þg1=2 . This function is plotted in Fig. 2.15.
with

through a finite rectangular barrier as
a function of incident energy. The
The transmission coefficient, T, takes on its maximum value of 1 and
curves are labelled with the value of the barrier is transparent when sin(k 0 L) ¼ 0, which occurs at energies E
Lð2mVÞ1=2 =
h. corresponding to1
np
k0 ¼ n ¼ 1, 2, . . . ð2:24aÞ
To obtain this result, we have used L
the first of the two relations Furthermore, T has minima near
eix  eix np
sin x ¼ k0 ¼ n ¼ 1, 3, . . . ð2:24bÞ
2i 2L
eix þ eix
cos x ¼ At high energies (E  V), T approaches its classical value of 1. We see in
2
Fig. 2.15 how the transmission coefficient for energies above the barrier
height fluctuates between maxima and minima.
We shall use the fact a number of We should take note of two striking differences between the quantum
times that sin x ¼ 0 at x ¼ np with mechanical and classical results. First, even when E > V, there is still a
n ¼ 0, 1, 2, . . . , and cos x ¼ 0 at probability of the particle being reflected by the potential barrier even though
x ¼ np/2, with n ¼ 1, 3, 5, . . . . classically it has enough energy to travel over the barrier. This phenomenon is
known as antitunnelling or non-classical reflection. Second, the strong vari-
ation of T with the energy of the incident particle is a purely quantum
mechanical effect. The peaks in the transmission coefficient for energies above
V are examples of scattering resonances. We shall have more to say con-
cerning resonances in Chapter 14 when we discuss scattering in general.

2.11 The Eckart potential barrier

The rectangular barrier we have been considering is obviously not very
realistic, but it does serve to introduce a number of concepts, and it has
properties that are found in more realistic models. In fact, there are only a few

.......................................................................................................

1. The value n ¼ 0 is excluded because in the limit of k 0 ! 0, T ¼ 1/(1 þ mVL2/2

h2), which is
not equal to 1.