Atkins & Friedman: Molecular Quantum Mechanics 5e

Chapter 14
Scattering Theory
All the following material P.W. Atkins and R.S. Friedman.
Exercises
14.1 (a) The process is inelastic because the electronic state of atomic oxygen changes.
(b) The process is elastic because the initial and final states are the same.
(c) The process is inelastic because the vibrational state of HF changes.
(d) The process is reactive because a chemical reaction has occurred; the reactant HF is
not retained in the product.
(e) The process is elastic because the initial and final states are the same.
Exercise: Characterize each of the following as elastic, inelastic or reactive:
O(
3
P
2
) + H
2
(v = 0, j = 0) O(
3
P
1
) + H
2
(v = 0, j = 0)
O(
3
P
2
) + H
2
(v = 0, j = 0) O(
3
P
2
) + 2H(
2
S)
14.2 For scattering by a one-dimensional potential energy barrier of finite width (Section 14.1),
the continuity conditions for the wavefunction and its slope at x = L are given by the last two
equations in eqn 14.1.
A
i
e
ikiL
+ B
i
e
ikiL
= A
ii
e
ikL
+ B
ii
e
ikL
(i)
ikA
i
e
ikiL
- ikB
i
e
ikiL
= ikA
ii
e
ikL
- ikB
ii
e
ikL
(ii)
Multiplying (i) by ik and adding (ii) yields:
Atkins & Friedman: Molecular Quantum Mechanics 5e


2ikA
ii
e
ikL
= ikA
i
e
ikiL
+ikA
i
e
ikiL
+ikB
i
e
ikiL
- ikB
i
e
ikiL

or
A
ii
=
e
i(k
|
-k)L
2k
(k + k
i
)A
i
+
e
i(k
|
-k)L
2k
(k - k
i
)B
i
e
2ik
|
L
(iii)
Similarly, multiplying (i) by ik and subtracting (ii) yields:
2ikB
ii
e
ikL
= ikA
i
e
ikiL
-ik
i
A
i
e
ik
|
L
+ikB
i
e
ik
|
L
+ ikB
i
e
ikiL

or
B
ii
=
e
i(k
|
-k)L
2k
(k - k
i
)A
i
e
2ikL
+
e
i(k
|
-k)L
2k
(k + k
i
)B
i
e
2ikL
e
2ik
|
L
(iv)
Equations (iii) and (iv) can be written in matrix form as
[
A
B
=
e
i(k
|
-k)L
2k
_
k + k (k -k
i
)e
2ik
|
L
(k - k
i
)e
2ikL
(k + k
i
)e
2ikL
e
2ik
|
L
_[
A
B

from which we confirm the form of the matrix Q given in Justification 14.1.

14.3 From eqns 14.2 and 14.3a:

[
B
A
= _
S
11
S
12
S
21
S
22
] [
A
B


If the particle is incident from the right of the one-dimensional barrier, then A = 0 (see Fig.

14.1 of the text). As a result:

B = S
12
B T = |S
12
|
2

Atkins & Friedman: Molecular Quantum Mechanics 5e


A = S
22
B R= |S
22
|
2

14.4 Use eqn 14.15
o = ,f
k
(u, |),
2
= sin
2
u cos
2
|
Exercise: Proceed to evaluate the integral scattering cross-section o
tot
.
14.5 Use eqn 14.7:
o
tot
=
2
0 0
C
} }
sinudud|
=
2
0 0
sin d C d u u |
( (

( (

} }

= 4tC
Exercise: What scattering amplitude f
k
corresponds to the above o
tot
? Within the Born
approximation, find the potential that gives rise to this scattering amplitude.
14.6 We show in Justification 14.2 that in the limit r , e
ikz
and f
k
e
ikr
/r are each eigenfunctions
of the hamiltonian with the same eigenvalue k
2

2
/2:. Therefore, the total wavefunction
has an asymptotic form given by the sum of e
ikz
and f
k
e
ikr
/r with eigenvalue k
2

2
/2::
H(e
ikz
+ f
k
e
ikr
/r) = H e
ikz
+ H f
k
e
ikr
/r
= (k
2

2
/2:) e
ikz
+ (k
2

2
/2:) f
k
e
ikr
/r
= (k
2

2
/2:)(e
ikz
+ f
k
e
ikr
/r)
14.7 The free-particle radial wave equation, eqn 14.23, is
2 0
2 0
2 2
d ( 1)
d
l
l
u l l
k u
r r
+
+
`
)
= 0
Atkins & Friedman: Molecular Quantum Mechanics 5e


(i)
0
0

( )
l
u j kr = = = sin(kr); l = 0 implies l(l +1)/r
2
= 0
2 0 2
2 2
d d sin( )
d d
l
u kr
r r
= = k
2
sin(kr)
Therefore
k
2
sin(kr) + {k
2
0} sin(kr) = 0
(ii)

0
l
u =
1
sin( )

( )
kr
j kr
kr
= cos(kr)

1

d ( )
d
j kr
r
=
2
cos( ) sin( ) kr kr
r kr
+ k sin(kr)

2
1
2

d ( )
d
j kr
r
=
2 3
sin( ) 2 cos( ) 2 sin( ) k kr kr kr
r r kr

+ + k
2
cos(kr)
Therefore

2 3
sin( ) 2 cos( ) 2 sin( ) k kr kr kr
r r kr
+ + k
2
cos(kr)
+
2
2
2 sin( )
cos( )
kr
k kr
kr r


` `
) )
= 0
Exercise: Repeat the confirmation for the first three (l = 0, 1, 2) RiccatiNeumann
functions.
14.8 The general relation between E and K is given in the equation proceeding eqn 14.51:

2
K
2
= 2:(E + V
0
)
Therefore
Atkins & Friedman: Molecular Quantum Mechanics 5e


E =
l
2
K
2
2p
- I
0

E
ies
=
l
2
K
ies
2
2p
- I
0

and, using eqn 14.62,
E
ies
=
(2n + 1)
2

2
l
2
8po
2
- I
0


14.9 The relation between the mean lifetime t of the resonance state and the full width at half-
maximum I is given by eqn 14.75. If the full width at half-maximum expressed in cm
1

units is denoted A, then I = hcA; therefore
t =
hcA

= (2tcA)
1

(a)
t = (2t 2.9979 10
10
cm s
1
0.05 cm
1
)
1

= 1.1 10
10
s = 0.11 ns
(b)
t = (2t 2.9979 10
10
cm s
1
3.5 cm
1
)
1

= 1.5 10
12
s = 1.5 ps
(c)
t = (2t 2.9979 10
10
cm s
1
45 cm
1
)
1

= 1.2 10
13
s = 0.12 ps
Atkins & Friedman: Molecular Quantum Mechanics 5e


Exercise: If the mean lifetime of the resonance state is 10 fs, what would be the expected
full width at half-maximum for the BreitWigner peak?

14.10 At scattering energy E
1
, the total number of open channels is 11 + 6 + 16 = 33. Therefore,
the scattering matrix is a 33 33 square matrix. The dimension is 33.
Exercise: Explore how the dimension of the scattering matrix varies with the scattering
energy. Take J = 0. Assume that only rotational levels in the ground vibrational states of
BC, AB, and AC are open. Treat the rotational constants of the three diatomic molecules
as equivalent.
14.11 We need to evaluate the integral on the right-hand side of eqn 14.102 assuming that the
cumulative reaction probability P(E) is independent of energy:
_ P(E)e
-Lk1
uE =

0
P _ e
-Lk1
uE

0

= -PkIe
-Lk1
|
0

= -PkI(u - 1)
= PkI
Therefore the rate constant is directly proportional to the temperature.
14.12 The classical model of chemical reactivity yields a cumultive reaction probability of
P(E) = 0 u E < I
0

P(E) = 1 I
0
E <
Therefore
k
i
(I) _ P(E)e
-Lk1
uE =

0
_ e
-Lk1
uE

v
0

Atkins & Friedman: Molecular Quantum Mechanics 5e


= -kIe
-Lk1
|
v
0

= kIe
-v
0
k1

This has a form similar to the Arrhenius equation if we allow the pre-exponential factor
A to be directly proportional to temperature and identify the activation energy E
a
with
E
a
/RT = V
0
/kT or, since R = kN
A
, E
a
= N
A
V
0
.

14.13 According to eqn 14.103 and the discussion in Section 14.10, a pole in the scattering
matrix (i.e. a resonance) will appear in each scattering matrix element. Therefore
scattering cross-sections connecting all possible incoming and outgoing channels should
have peaks at the same energy E
res
with the same width I. In this case, the resonance
which appears in the neutronTe scattering process effects both the elastic scattering and
non-elastic scattering processes and therefore the cross-sections show BreitWigner peaks
at the same energy and of the same width.
Exercise: It is found experimentally that the scattering cross-sections have peaks at an
energy of 2.3 eV with a width of 0.11 eV. Determine the resonance energy of the
resonance state in the neutronTe scattering process.

14.14 The scattering matrix S is often symmetric, S
ij
= S
ji
. (It is always symmetric when the
scattering process has a property known as time-reversal invariance). The probability in
general for a transition from incident channel i to final channel j is given by
P
ji
= ,S
ji
,
2

Thus, for a two-channel scattering process with a symmetric scattering matrix,
Atkins & Friedman: Molecular Quantum Mechanics 5e


P
12
= ,S
12
,
2

= ,S
21
,
2

= P
21

consistent with the principle of microscopic reversibility.
Exercise: Give examples of scattering systems for which the principle of microscopic
reversibility is not satisfied.

Problems
14.1 For Zone II (see Section 14.1), the potential energy is V(x) = V (rather than +V) and all
solutions are oscillatory for positive energies:
Zone II: = A'e
iKx
+ B'e
iKx
K = {2m(E + V)}
1/2

Hence S can be constructed from eqn 14.3 by replacing k' in eqn 14.3c with K. The
transmission probability for a particle incident from the left is given by |S
21
|
2
.
14.4. From Example 14.3
o =
2 2 4
0
2 2 2 2
1
2
4 /
( 4 sin )
V
k

o u +


=
2 2
0
4 4 2 2 2 2
1
2
4
(1 (4 / )sin )
V
k

o o u +


2 2 2
0
(2 / ) V
o
o
=
2 2 2 2
1
2
1
(1 (4 / )sin ) k o u +

(a) For zero energy, k = 0
Atkins & Friedman: Molecular Quantum Mechanics 5e


2 2 2
0
(2 / ) V
o
o
= 1
independent of u.
(b) For moderate energy (k = o/2)
k
2
/o
2
=
1
4


2 2 2
0
(2 / ) V
o
o
=
2 2
1
2
1
(1 sin ) u +

(c) For high energy (k = 10o)
k
2
/o
2
= 100

2 2 2
0
(2 / ) V
o
o
=
2 2
1
2
1
(1 400sin ) u +

Plots of the differential cross-section as a function of 2 are shown in Fig. 14.1 for (a), (b)
and (c). For k >> o, o falls off very rapidly as u increases from 0 to t/2.



Fi
ap
en
Ex
14.7 To
Si

At
igure 14.1 Th
pproximation
nergy (k = 10
xercise: Com
derive eqns
C
r
ince
tkins & Frie
he differenti
n for (a) zero
0o).
mpare the pl
14.41 and 1
1
2
sin(
l
C
kr l
r

edman: Mol
ial cross-sect
o energy (k =
lots to those
4.42, we beg
) (2
l
l
l i o + =
sin x =
e
ecular Qua

tion for the Y
= 0), (b) mod
for k = o an
gin with the
sin(
2 1)
kr
l
k
+
i i
e e
2i
x x

antum Mech
Yukawa pot
derate energ
nd k = 20o.
equation fol
1
2
) e
l
l
f
kr

+
hanics 5e
tential within
gy (k = o/2),
llowing eqn
i
e
kr
r


n the Born
and (c) high
14.40
h
Atkins & Friedman: Molecular Quantum Mechanics 5e



1 1
2 2
i( ) i( )
e e
2i
l l
kr l kr l
l
C
r
o o + +

=
1 1
2 2
i( ) i( )
i
e i (2 1)[e e ]
2i
kr l kr l
kr l
l
f l
kr r

+
+
Collect terms with a common factor of e
ikr

1
2
1
2
i
i
i
i i
e e (2 1)
e e e
2i 2i
l
l
l
kr kr l
C i l
r kr
i
o



+
=
` `

)
)

Cancel common terms:
i
i (2 1)
e
l
l
l
l
C
k
o
+
=
or
i
i (2 1)
e
l
l
l
l
C
k
o
+
= [eqn 14.41]
Now collect terms with a common factor of e
ikr

1 1
2 2
i i
i
i i
e e i (2 1)e
e e
2i 2i
l
l l
l
kr kr l l
C f l
r kr r
o


+
= +
` `

) )

Cancel common terms:
1 1
2 2
i i
i
e e i (2 1)e
2i 2i
l
l l
l
l l
l
C f
k
o

+
= +
Use eqn 14.41:
Atkins & Friedman: Molecular Quantum Mechanics 5e


1 1
2 2
i i
i i
i (2 1)e e e i (2 1)e
2i 2i
l l
l l
l l
l
l l
f
k k
o o

+ +
= +
Because e
it/2
= i, e
itl/2
= i
l
.
Therefore
2i
(2 1)e (2 1)
2i 2i
l
l
l l
f
k k
o
+ +
= +
f
l
=
2i
(2 1)
(e 1)
2i
l
l
k
o
+

=
i i
i
(2 1) (e e )
e
2i
l l
l
l
k
o o
o

+


=
i
(2 1)
e sin
l
l
l
k
o
o
+
[eqn 14.42]
Exercise: Derive eqn 14.49.

14.10
If V(r) > 0 for all r, then o
l
(E) < 0.
If V(r) < 0 for all r, then o
l
(E) > 0.
Note that if V(r) = 0, o
l
(E) = 0 by definition.
If the potential is purely repulsive for all r, then, since the energy E of the particle is
conserved in elastic scattering, the particles kinetic energy is decreased as a result of
scattering. The wavelength of the particle is therefore increased (recall = h/p),
Atkins & Friedman: Molecular Quantum Mechanics 5e


corresponding to a negative phase shift o
l
. (Recall that sin(kr + o) has a longer wavelength
than sin kr if o < 0.)
Conversely, if the potential is purely attractive for all r, the particle is accelerated as it
scatters. The increase in kinetic energy corresponds to a shortened wavelength and a
positive phase shift o
l
.
Exercise: Sketch the form of the scattering wavefunctions for V(r) > 0, V(r) = 0, and V(r)
< 0; qualitatively verify the above conclusions.
14.13
V(r) =
0
if 0
if 0
0 if
r
V r a
r a
=

< <

>

Consider energies E > V
0
and find o
0
.
At r = 0, V(r) = which implies u
0
(0) = 0 for the radial wavefunction.
For 0 < r < a, V(r) = V
0
(V
0
> 0)
2 2
0
2
d
2 d
u
m r

+ V
0
u
0
= Eu
0
(centrifugal potential = 0)
2
0
2 2
d 2
d
u m
r
+

(E V
0
)u
0
= 0
u
0
(r) = A sin k
1
r + B cos k
1
r
2
1
k =
2
2m

(E V
0
)
For r > a, V(r) = 0
Atkins & Friedman: Molecular Quantum Mechanics 5e


2 2
0
2
d
2 d
u
m r

= Eu
0

u
0
(r) = C sin kr + D cos kr
k
2
=
2
2mE

As r
u
0
(r) = C sin kr + D cos kr
= E sin(kr + o
0
)
where
tan o
0
= D/C
To find o
0
, we need to obtain an expression for D/C. We require that u
0
(r) and (du
0
/dr) are
continuous at r = a.
First, require u
0
(r) be continuous at r = 0. (We do not impose continuity of (du
0
/dr) at r =
0 because V(0) = .)
r = 0 : u
0
(r = 0) = 0 = A sin k
1
0 + B cos k
1
0 = B
Therefore for 0 < r < a, u
0
(r) = A sin k
1
r
r = a : u
0
(r = a) = A sin k
1
a = C sin ka + D cos ka
0
d
d
u
r
(r = a) = k
1
A cos k
1
a = kC cos ka kD sin ka
Divide the above two equations:
Atkins & Friedman: Molecular Quantum Mechanics 5e



1
1
k
tan k
1
a =
sin cos
cos sin
C ka D ka
kC ka kD ka
+

=
sin ( / ) cos
cos ( / ) sin
ka D C ka
k ka k D C ka
+

=
0
0
sin tan cos
cos tan sin
ka ka
k ka k ka
o
o
+

1
k
k
tan k
1
a cos ka
1
k
k
tan k
1
a tan o
0
sin ka = sin ka + tan o
0
cos ka
1
k
k
tan k
1
a cos ka sin ka = tan o
0

1
1
cos tan sin
k
ka k a ka
k

+
`
)

tan o
0
=
1 1
1 1
( / ) tan cos sin
( / ) tan sin cos
k k k a ka ka
k k k a ka ka

+

with
1/ 2
1 0
k E
k E V
| |
=
|
\ .

Exercise: First, plot o
0
as a function of E (E > V
0
) for fixed V
0
and a. Second, for E > V
0
,
find an expression for the P-wave phase shift o
1
for scattering off the same central
potential and plot o
1
as a function of energy.

14.16 The spherical square well potential is given in Section 14.5: V = V
0
for r s a and V = 0
for r > a. We solve this problem by requiring that the radial solution u
l
(r) and its first
derivative be continuous at r = a.
Atkins & Friedman: Molecular Quantum Mechanics 5e


In the region r s a, we have to solve the equation
2
2
2 2
d ( 1)
0
d
l
l
u l l
K u
r r
+ (
+ =
(


where

2
K
2
= 2(E + V
0
)
The general solution is a linear combination of the RiccatiBessel and RiccatiNeumann
functions:
u
l
(r) = A
l

l
(Kr) +A
I
i
n
I
(Kr)
To ensure that R(r) = u
l
/r is finite at the origin, we require u
l
(0) = 0. Since the Riccati
Neumann function n
l
(z) behaves like z
l
as z 0, we must have
l
A' = 0. Therefore, inside
the well the solution is of the form
u
l
(r) = A
l

l
(Kr)
For r > a, the potential vanishes and u
l
is the solution of the free-particle equation (which
includes the l(l + 1)/r
2
centrifugal potential term). We can immediately write down the
solution as
u
l
(r) = C
l

l
(kr) + D
l
n
l
(kr)
where, as usual, E = k
2

2
/2. The scattering phase shift o
l
is introduced via
C
l
= B
l
cos o
l
D
l
= B
l
sin o
l

Atkins & Friedman: Molecular Quantum Mechanics 5e


so we can write
u
l
(r) = B
l
cos o
l

l
(kr) + B
l
sin o
l
n
l
(kr)
We require that u
l
(r) and its first derivative be continuous at r = a. The continuity of the
wavefunction requires that
A
l

l
(Ka) = B
l
cos o
l

l
(ka) + B
l
sin o
l
n
l
(ka)
and the continuity of the first derivative requires that
KA
l

I
i
(Ka) = kB
l
cos *
l

I
i
(ko) + kB
l
sin*
l
n
I
i
(ko)
where the prime denotes the derivative with respect to r. Division of the above two
equations results in the following complicated expression for the phase shift:
K

I
i
(Ko)

I
(Ko)
= k

I
i
(ko) + tan o
I
n
I
i
(ko)

I
(ko) + tan o
I
n
I
(ko)

or
tan o
I
=
K
I
i
(Ko)
I
(ko) -k
I
(Ko)
I
(ko)
k
I
(Ko)n
I
i
(ko) - K
I
i
(Ko)n
I
(ko)

From the above equation, for a given energy (and corresponding K and k), we can
determine the phase shift o
l
.
Exercise: Write down the expression for o
l
for P-wave scattering by a spherical square-
well potential.

Atkins & Friedman: Molecular Quantum Mechanics 5e


14.19 Begin with the asymptotic expression (eqn 14.92) for the multichannel stationary
scattering state
+
o0
-
A
0
0 0
i
i
A
e
e
k r
k z
f
r
o
o
o oo o
o
_ _ +

The incident flux J
i
is determined by the plane wave e
iko
0
z
which is the term containing all
the (relative) initial kinetic energy. By analogy with the results in Justification 14.3, the
magnitude of the incident flux is k
o
0
/.
Likewise, by analogy with the result for J
r
in Justification 14.3,
J
r
=
2
2
| |
k
k f
r

for the radial component of the flux density corresponding to (f
k
e
ikr
/r), we have here
J
r
=
0
2
2
| | k f
r
o oo

where we have equated r
A
with r, the relative position.
Only J
r
needs to be retained as r and we have focused on a single term o in the
summation for
o
0
.
Following the argument in Section 14.3, we then have
dN
s
= J
r
r
2
dO
Atkins & Friedman: Molecular Quantum Mechanics 5e


=
0
2
| |
d
k f
o oo
O

=
0
d
i
J
oo
o O


=
0
0
d
k
o
oo
o O

and therefore
0 0
0
2
| |
k
f
k
o
oo oo
o
o =
Exercise: Show in detail why _
o
and _
o
0
do not need to be considered in the above
argument and also why we can treat each term o in the summation of eqn 14.92
individually.


14.22 (i) Model the cumulative reaction probability as P(E) = arctan(E).
(a) In the limit E 0, P = arctan(0) = 0, consistent with the model.
(b) At E = V
0
, P = arctan( V
0
) =.
(c) In the limit E , P = arctan() = B/2 = 1.
From condition (c), = 2/B. Therefore, from condition (b),
(2/B) arctan( V
0
) =
arctan( V
0
) = B/4
V
0
= 1 [since tan B/4 = 1]
= 1/ V
0

Atkins & Friedman: Molecular Quantum Mechanics 5e


(ii) Model the cumulative reaction probability as P(E) = 1 e
E
.
(a) In the limit E 0, P = 1 1 = 0, consistent with the model.
(b) At E = V
0
, P = 1 - e
-uv
0
= V
(c) In the limit E , P = 1 0 = 1, consistent with the model.
From condition (b), e
-uv
0
= V or = (ln 2)/V
0
.
For part (ii), the temperature dependence of the rate constant predicted by eqn 14.102 is
k
i
(I) _ P(E)e
-Lk1
uE =

0
_ (1 e
-uL
)e
-Lk1
uE

0

= _ e
-Lk1
uE - _ e
-L(u+1k1)

0
uE

0

= -kIe
-Lk1
|
0

+
1
o + 1kI
e
-L(u+1k1)
|
0

= kI -
1
o + 1kI

= kI -
1
(ln2I
0
) +(1kI)

= kI _1 -
1
kI(ln 2I
0
) + 1
_
= kI _1 -
I
0
kI ln2 + I
0
_