TOPIC 7D Translational motion

Discussion questions
D7D.1 Explain the physical origin of quantum mechanical tunnelling. Why is tunnelling more
likely to contribute to the mechanisms of electron transfer and proton transfer processes than to
mechanisms of group transfer reactions, such as AB + C → A + BC (where A, B, and C are
large molecular groups)?
ANS: 有關穿隧效應(tunnelling)的物理的源始是粒子概率密度(probability density)大小, 根據 "波恩"對波函數的

註解(Born interpretation) , 粒子出現的概率密度是其波函數的平方。這種解釋的要件也侷限了系統的波函數 ,在

任何地方都是連續的,即使是陷於壁障中的狀態亦是連續的。因此, 如果波函數在壁障的一側為非零, 且在壁障

的另一側亦為非零, 這意味著粒子已通過屏障隧道。

穿透的傳輸概率取決於粒子的質量 (精確的說, 是 m1/2): 質量越大, 穿隧的概率就越小。電子和質子有小的質

量, 分子群則有大的質量;因此, 當在涉及電子和質子的過程中, 隧道效應更容易被觀察到。(The physical origin

of tunnelling is related to the probability density of the particle, which according to the Born interpretation is the

square of the wavefunction that represents the particle. This interpretation requires that the wavefunction of the

system be everywhere continuous, even at barriers. Therefore, if the wavefunction is non-zero on one side of a barrier

it must be non-zero on the other side of the barrier and this implies that the particle has tunnelled into the barrier. The

transmission probability depends upon the mass of the particle: the greater the mass the smaller the

probability of tunnelling. Electrons and protons have smaller masses, molecular groups larger masses;

therefore, tunnelling effects are more observable in process involving electrons and protons.)

D7D.2 Explain the physical origin of quantization for a particle confirmed to the interior of a
one-dimensional box.
ANS: 在量子力學中。認為自由粒子,即一個具有零勢能的粒子, 的 Schrödinger 方程式,是由形式 ψ = sin kx 的
波函數求解,相對應的能量為 k 2 ℏ2/2m, 其中的 k 可為任何值。此解適用於箱內,但由於勢能於框外無窮大,在這
些區域中,波函數必須為零。在盒子的牆壁上,波函數必須是連續的,因此,當盒子內的波函數進入牆壁時,它必須

達到零。假設牆位於 x = 0 和 x = L, 則僅當 k = nπ/L (其中 n 是正整數, n = 1、2、......)的條件滿足時才成立。

因此,所得到量子化的能量,是依 E = n2 π 2 ℏ2 的離散值。
2 m L2
The Schrödinger equation for a free particle, that is one experiencing zero potential energy, is solved by
functions of the form ψ = sin kx for any value of k. The corresponding energy is k 2 ℏ2/2m. This solution
applies inside the box but, because the potential goes to infinity outside the box, in these regions the
wavefunction must be zero. At the walls of the box the wavefunction must be continuous, and therefore as
the wavefunction inside the box goes to the walls it must go to zero. Assuming that the walls are at x = 0
and x = L this condition is only satisfied if k = nπ/L, where n = 1, 2, …. The energy is therefore quantized

with values n2 π 2 ℏ 2 .
2 m L2

D7D.3 Describe the features of the solution of the particle in a one dimensional box that appear
in the solutions of the particle in two- and three- dimensional boxes. What feature occurs in the
two- and three- dimensional box that does not occur in the one-dimensional box?
ANS: 由於二維或三維的平移運動可以經變數分離成為獨立的兩個一維運動, 因此得以延續一維的解的許多
特徵。例如,在每個維度中發生的量子化, 就像在一維情況下一樣;在每個維度中的能量與一維情況下的能量具

有相同的形式; 運動相關的一維波函數是多維波函數中的因數。簡併的概念是: “一個具有相同能量的多個不

同的波函數”; 對於一維盒中粒子來說是不會出現的, 但它可能出現在多維的情況下 (取決於盒子的比例)。例

如, 在二維方形框中, (n1, n1) = (1,2) 的狀態 (n1 = 1 和 n2 = 2)與(n1, n1) = (2,1) 的狀態 (n1 = 2 和 n2 = 1)具有相同

的能量。The hamiltonian for a particle in a two- or three-dimensional box is separable into a sum of terms

each of which depends on just one of the variables x, y or z. Therefore the solutions to the Schrödinger
equation are products of separate functions of each of these variables,
Ψ(x, y, z) = ψ(x)ψ(y)ψ(z). In the hamiltonian the terms in the three variables are all of the same form,
so the wavefunctions are likewise of the same form. Similarly, the boundary conditions along each
direction are the same, so the quantization which this imposes is the same. As a result the wavefunctions
are simply a product of the wavefunctions that would be found by solving the Schrödinger equation along
each direction separately.
The energy levels of two- and three-dimensional boxes can be degenerate, that is, there are different
wavefunctions which have the same energy. This is usually a consequence of the box having a certain
kind of symmetry, for example in a two-dimensional box in which the two sides are the same length the
levels with quantum numbers n1 = l, n2 = m and n1 = m, n2 = l are degenerate.

Exercises

E7D.1(a) For a particle in a box of length L, write the expression for the energy levels, En, and
then write a similar expression En’ for the energy levels when the length of the box has increased
to 1.1L (that is, an increase by 10 per cent). Calculate (En’ – En) / En, the fractional change in the
energy that results from extending the box.
n2 h 2 1 h2
ANS: The energy levels of a PIB with length L, En =
8m L 2
L ( )
=K 2 , K=n 2
8m
1
when the length is increased to 1.1 ×L the energies become, En ' =K
( ( 1.1 L )2 )
'
Hence the relative change is En−E n 1 = –0.174 or –17.4 %
En
=
( ( 1.1 ) 2
)−1

E7D.1(b) Repeat the calculation in Exercise E7D.1(a) but this time for a cubical box of side L
and for a decrease to 0.9L (that is, a decrease by 10 per cent).
n2 h 2 1 h2
ANS: In the original cubic box, En =
8m L 2
=K 2 ,
L ( ) K=n 2
8m
 1
When the side is decreased to 0.9 ×L the energies become En ' =K ( ( 0.9 L )2 )
Hence E'n −En=¿

∆E 1
and the relative change is
En
=
( 0.9 )2 ( )
−1 =0.235=23.5 %

E7D.2(a) Find an expression for the value of n of a particle of mass m in a one-dimensional box
of length L such that the separation between neighboring levels is equal to the mean energy of
thermal motion (½ kT). Calculate the value of n for the case of a helium atom in a box of length
1 cm at 298 K.
ANS: If the separation between neighboring levels is equal to the average thermal energy,
2 2 h2 h2 kT
∆ E n=En +1−En =[ ( n+1 ) −n ] = .
❑
2
= ( 2 n+1 ) 2
8mL 8mL 2

Solve for n, 2 n+1= 8 mkT L2 and 2 m L2 kT 1 .

n= −
2 h2 h2 2
For a helium atom, mass 4.00 mu in a box for length 1 cm,
2
J ( 0.01 m 1
n=2 ( 4.00 ×1.6605 ×10−27 kg ) 1.381 ×10−23 ( K ) (
298 K ) −34
6.626 ×10 J s
−
2 )
¿ 1.24 ×10 16
E7D.2(b) Find an expression for the value of n of a particle of mass m in a one-dimensional box
of length L such that the energy of the level is equal to the mean energy of thermal motion (½ kT
). Calculate the value of n for the case of an argon atom in a box of length 0.1 cm at 298 K.
2 2
ANS: The energy is En = n h , . If the energy of the level is equal to the average thermal
2
8m L
2 2
n h kT 8 m L2 kT 2 L
energy when =
8 m L2 2
Solve for n, n=
2h 2
=
h √
√mkT
For an argon atom in a box of length 0.1 cm at 298 K, m = 39.95 mu, L = 0.001 m, T = 298 K, we
got
2L 2 × ( 0.001 m ) 1/ 2
n= √ mkT = ( 39.95× 1.6605× 10−27 kg ×1.381 ×10−23 J K−1 × 298 K )
h 6.626 × 10 J s
−34

= 5.0 ×107
E7D.3(a) For a particle in a square box of side L, at what position (or positions) is the
probability density a maximum if the wavefunction has n1 = 2, n2 = 2 ? Also, describe the
position of any node or nodes in the wavefunction.
ANS: The wavefunction of a particle in a square box of side length L with quantum
numbers n1 = 2, n2 = 2 is ψ 2,2 ( x , y )= 2 sin 2 πx sin 2 πy .
(L) ( L ) ( L )
2
2 2 πx 2 πy
P ( x , y )=( ) sin ( ) sin (
L )
The probability density is 2 2
2,2
L L

The probability density is maximized when sin 2 πx sin 2 πy =1, which

(L) (L) 2 2

occurs only when each sin term is equal to ±1.

sin ( 2 Lπx )=±1 ; 2Lπx = π2 , 32π hence x= L4 , 34L , and similarly for y y= L4 , 34L .
Hence the maxima in probability density occurs at (x, y)

¿ ( L4 , L4 ) ,( L4 , 34L ) ,( 34L , L4 ) ,( 34L , 34L ) .

Nodes occur when the wavefunction passes through zero, which is when either of the sin terms
are zero, excluding the boundaries at x = 0, L; y = 0, L because at these points the wavefunction
does not pass through zero. There is thus a node when sin (2πx/L) = 0, corresponding to x = L/2
and any value of y. This node is therefore a line at x = L/2 and parallel to the y axis . Similarly
there is another nodal line at y= L/2 and parallel to the x axis.

E7D.3(b) For a particle in a square box of side L, at what position (or positions) is the
probability density a maximum if the wavefunction has n1 = 1, n2 = 3? Also, describe the
position of any node or nodes in the
wavefunction.
ANS: The wavefunction of a particle in a square box of side length L with quantum

numbers n1 = 1, n2 = 3 is ψ 1,3 ( x , y )= 2 sin πx sin 3 πy .

(L) ( L ) ( L )
2
2 πx 3 πy
P ( x , y )=( ) sin ( ) sin (
L )
The probability density is 2 2
1 ,3
L L

The probability density is maximized when sin πx sin 3 πy =1,

(L) ( L ) 2 2

which occurs only when each sin term is equal to ±1.

The term in x is equal to 1 when πx/L = π/2 and hence x = L/2, and similarly for y:

( 3 Lπy )=± 1; 3 Lπy = π2 , 32π , 52π hence y= L6 , 36L , 56L ,

sin

Hence the maxima in probability density occurs at (x, y)¿ L , L , L , L , L , 5 L

(2 6) (2 2) (2 6 )
Nodes occur when the wavefunction passes through zero, which is when either of the sin terms are zero,
excluding the boundaries at x = 0, L y = 0, L because at these points the wavefunction does not pass
through zero. There are therefore no nodes associated with the function sin (πx/L). In the y-direction there
are nodes when sin
( 3 Lπy )=0 ; 3Lπy =π , 2 π hence y= L3 , 23L
There is thus a node when y = L/3 and for any value of x, that is a nodal line at y = L/3 and parallel to the
x-axis. Likewise the node at y = 2L/3 corresponds to a nodal line at y = 2L/3 and parallel to the x-axis .

E7D.4(a) For a particle in a rectangular box with sides of length L1= L and L2= 2L, find a state
that is degenerate with the state n1= n2 = 2. (Hint: You will need to experiment with some
possible values of n1 and n2) Is this degeneracy associated with symmetry?

ANS: The energy levels are given by

We are looking for another state that has the same energy. By inspection we note that the first

term in parentheses in E2,2 works out to be 4 and the second 1: E2,2 =( 4 +1 ) h2 h2

=5
8 m L2 8 m L2

We can arrange for those values to be reversed: E1,4 =( 1+4 ) h2 h 2 The question
=5 .
8 m L2 8 m L2
notes that degeneracy frequently accompanies symmetry. In this system, a state (n1, n2) is
degenerate with a state (n2/2, 2n1) as long as (a) the latter state exists (i.e., n 2/2 must be an
integer), and (b) is distinct from (n1, n2).

E7D.4(b) For a particle in a rectangular box with sides of length L1= L and L2= 2L, find a state
that is degenerate with the state n1=2, n2 = 8. Would you expect there to be any degenerate states
for a rectangular box with L1= L and L2= √2L,? Explain your reasoning.
ANS: The energy levels for a 2D rectangular box, side lengths L1= L, L2 = 2L are given by

We are looking for another state that has the same energy. By inspection we note that the first
term in parentheses in E2,8 works out to be 4 and the second 16; we can arrange for those values
to be reversed: a state (n1, n2) is degenerate with a state (n2/2, 2n1),
4 2 4 2 h2 h2 20 h2
E 4,4= ( + )
1 4 8 m L2
= ( 16+ 4 ) =
8 m L2 8 m L 2
So in this box, the state n1=4, n2=4 is degenerate to the state n1=2, n2=8.
The energy levels for a 2D rectangular box, side lengths L1= L, L2 = √2L are given by
 n12
n22 h 2 n12 n22 h2 22 82 h 2 h2 9 h2
1 2
(
En , n = 2 + 2
L1 L2 8 m
=
) (
1
+ E =) +
2 8 m L2 2,8 1 2 8 m L2
= ( 4(+32 ) ) =
8 m L 2 2 m L2

A box with incommensurable sides, say, L and 2½ L, would have no degenerate levels.

E7D.5(a) Consider a particle in a cubic box. What is the degeneracy of the level that has an
energy three times that of the lowest level?

ANS: The energy levels are En1,n2,n3 =

where E1 combines all constants besides quantum numbers. The minimum value for all the
quantum numbers is 1, so the lowest energy is E1,1,1 = 3E1. The question asks about energy 3
times this amount, namely 9E1. This energy level can be obtained by any combination of
allowed quantum numbers such that n12 + n22 + n32 = 9 = 22 + 22 + 12. The degeneracy, then, is 3,
corresponding to (n1, n2, n3) = (1, 2, 2), (2, 1, 2), or (2, 2, 1).
E7D.5(b) Consider a particle in a cubic box. What is the degeneracy of the level that has an
energy 14/3 times that of the lowest level?

ANS: The energy levels are En1,n2,n3 =

where E1 combines all constants besides quantum numbers. The minimum value for all the
quantum numbers is 1, so the lowest energy is E1,1,1 = 3E1. The question asks about energy 14/3
times this amount, namely (14/3)×(3E1) = 14E1. This energy level can be obtained by any
combination of allowed quantum numbers such that n12 + n22 + n32 = 14 = 32 + 22 + 12. The
degeneracy, then, is 6, corresponding to (n1, n2, n3) = (1, 2, 3), (2, 1, 3), (1, 3, 2), (2, 3, 1), (3, 1,
2), or (3, 2, 1).

E7D.6(a) Suppose that the junction between two semiconductors can be represented by a barrier
of height 2.0eV and length 100 pm. Calculate the transmission probability of an electron with
energy 1.5eV.
ANS:

E7D.6(b) Suppose that a proton of an acidic hydrogen atom is confined to an acid that can be
represented by a barrier of height 2.0eV and length 100 pm. Calculate the probability that a
proton with energy 1.4eV can escape from the acid.
ANS: The transmission probability T depends on the energy of the tunneling particle relative to the
barrier height ( = 0.75), the width of the barrier, (L = 100 pm), and the decay parameter of the
wavefunction inside the barrier (𝜅),
 and

E7D.7(a) Evaluate the linear momentum and kinetic energy of a free electron described by the
wavefunction. eikx with k = 3 nm–1
ANS: If the wavefunction is an eigenfunction of an operator, the corresponding eigenvalue is the

value of corresponding observable [Topic 7C.1(b)]. Applying the linear momentum operator

to the wavefunction yields so the wavefunction

is an eigenfunction of the linear momentum; thus, the value of the linear momentum is the

eigenvalue

ℏk = 1.055 ×10–34 J s × (3 nm–1) × (1 ×109 m–1/ nm–1) = 3.165 ×10–25 kg m s–1

Similarly, applying the kinetic energy operator to the wavefunction yields

so the wavefunction is an eigenfunction of this operator as well; thus, its value is the eigenvalue
2
( ℏk )2 ( 1.055 ×10 – 34 J s × 3× 109 m – 1 )
Ek = = =5.6 ×10−20 J
2m 2× 9.019 ×10 kg −31

E7D.7(b) Evaluate the linear momentum and kinetic energy of a free proton described by the
wavefunction e–ikx with k = 5 nm–1.
ANS: If the wavefunction is an eigenfunction of an operator, the corresponding eigenvalue is the value

of corresponding observable. Applying the linear momentum operator ℏ d to the wavefunction

^p=
i dx

yields ℏ d ℏ d −ikx
^p ψ= ψ= e =( ℏk ) e−ikx , so the wavefunction is an eigenfunction of the linear
i dx i dx
momentum; thus, the value of the linear momentum is the eigenvalue:
p = ℏk = 1.055 ×10–34 J s × (5 nm–1) × (1 ×109 m–1/ nm–1) = 5 ×10–25 kg m s–1

^ −ℏ2 d 2 to the wavefunction yields

Similarly, applying the kinetic energy operator Ek =
2 m dx 2
2
−ℏ2 d 2 −ℏ 2 d 2 −ikx ( ℏk ) −ikx so the wavefunction is an eigenfunction of this
Ek ψ=
^ ψ= e = e
2 m dx 2 2 m dx 2 2m
operator as well; thus, its value is the eigenvalue.
 2
( ℏk )2 ( 1.055 ×10 – 34 J s ×5 × 109 m – 1 )
Ek = = =8 ×10 – 23 J
2m 2× 1.67× 10 kg−27

E7D.8(a) Write the wavefunction for a particle of mass 2.0 g travelling to the left with kinetic
energy 20 J.
ANS: The wavefunction for the particle travelling to the left is ψ k = Ae−ikx [7D.2 with B = 0].

The index k is given by . For the a 2.0 g particle travelling with kinetic energy 20 J.

Solving for k, the index k is given by the relationship

k=
√2 m E k = √2 ( 2.0 ×10−3 kg ) × ( 20 J ) = 2.7 ×10 33 m– 1
ℏ 1.055 ×1 0 – 34 J s

E7D.8(b) Write the wavefunction for a particle of mass 1.0 g travelling to the right at 10 m s–1.
ANS: The wavefunction for the particle moving toward positive x is ψ k = Aeikx [7D.2 with B =

0]. The index k is given by . But the kinetic energy of a 1.0 g particle travelling at 10

m s−1 is . By equating these two expressions and solving for k, the index k is given

−3 –1
p mv ( 1.0 × 10 kg ) × ( 5 ms )
by the relationship k = = = – 34
= 9.5 ×10 31 m – 1
ℏ ℏ 1.055 ×1 0 J s
31 −1

ψ=ei ( 9.5 ×10 m )x

E7D.9(a) Calculate the energy separations in joules, kilojoules per mole, electronvolts, and
reciprocal centimeters between the levels (i) n = 2 and n = 1, (ii) n = 6 and n = 5 of an electron
in a box of length 1.0 nm.
( n h )2
ANS: E=
8 m e L2
2
h2 ( 6.626 ×10−34 Js ) =
2
= 2 6.02 ×10−20 J
8 m e L 8 ( 9.109 × 10 kg ) ( 1.0 ×10 m . )
−31 −9

( n+ 1 )2 h2 n2 h2 h2
En +1−En = − = ( 2 n+1 )
8 m L2 8 m L2 8 m L2

The conversion factors required are

2 ( h )2 2
(i) n = 2 and n = 1, E2– E1 = ( 2 −1 ) 2
=3× 6.02× 10−20 J = 1.806×10−19 J
8 me L
 = 108.7 kJ mole−1 = 1.13 eV = 9090 cm−1
2 2 ( h )2
(ii) n = 6 and n = 5; E6– E5 = ( 6 −5 ) =11 ×6.02 ×10−20 J = 6.620×10−19 J
8 m e L2
= 399 kJ mole−1 = 4.13 eV = 33300 cm−1

E7D.9(b) Calculate the energy separations in joules, kilo joules per mole, electronvolts, and
reciprocal centimeters between the levels (i) n = 3 and n = 2, (ii) n = 7 and n = 6 of an electron
in a box of length 1.50 nm.
ANS:
2 =
( n h )2 2 ( 6.626 ×10−34 Js )
E= =n n2 ×
8 m e L2 −31 −9 2
8 ( 9.109 ×10 kg ) ( 1.5 ×10 m. )
E2 – E1 = 1.806 x 10–19 J
2.68×10−20 J

2 2 ( h )2
(i) n = 3 and n = 2, E3 – E2 = ( 3 −2 ) =5 ×2.68 ×10−20 J = 1.34×10−19 J = 80.7
8 m e L2
kJ mole−1 = 0.84 eV = 6750 cm−1
( h )2
2 2
(ii) n = 7 and n = 6; E7 – E6 =( 7 −6 ) 2
=13 ×2.68 × 10−2 0 J = 3.48×10−19 J = 210
8 me L
kJ mole−1 = 2.17 eV = 1750 cm−1

The conversion factors required are

1 eV = 1.602×10–19 J; 1 cm–1 = 1.986×10–23 J; 1 eV = 96.485 kJ mol–1

E7D.10(a) For a particle in a one-dimensional box, show that the wavefunctions Ψ1 and Ψ2 are
orthogonal. The necessary integrals will be found in the Resource section.
1/ 2 1/ 2
ANS:Ψ 1= 2 π x and
( L) ( ) sin
L
Ψ 2=
2
L ( ) sin ( 2 πL x )
sin ( a−b ) x sin ( a+b ) x
∫ sin ( ax ) sin ( bx ) dx= 2 ( a−b )
−
2 ( a+b )
Use formula: to evaluate the integral:
 ∫0 Ψ 2 Ψ 1 dτ =( 2L )∫0 sin (2Lπ x ) sin ( πL x ) dx
L L

L
π π
¿
2
(
sin ( 2−1 ) x sin ( 2+1 ) x
L
L 2 ( 2−1 )
−
L
2 ( 2+1 )
L
)0

2 1 π 1 π
¿
L 2 ( ( ) ( ))
sin x − sin 3 x
L 6 L 0

2
¿
L (12 sin ( π )−16 sin (3 π )− 12 sin ( 0 )+ 16 sin ( 0) )
2 0 0 0 0
¿
L (2 −6 −2 +6 )=0
E7D.10(b) For a particle in a one-dimensional box, show that the wavefunctions Ψ1 and Ψ3 are
orthogonal.
1/ 2 1/ 2
ANS: :Ψ 1= 2 π x and
( L) ( ) sin
L
Ψ 3=
2
L ( ) sin ( 3 πL x )
sin ( a−b ) x sin ( a+b ) x
∫ sin ( ax ) sin ( bx ) dx= 2 ( a−b )
−
2 ( a+b )
Use formula: to evaluate the integral:

where sin nπ = 0 for integer n

is used. The two
wavefunctions are
orthogonal.

E7D.11(a) Calculate the probability that a particle will be found between 0.49L and 0.51L in a
box of length L for (i) Ψ1 (ii) Ψ2. You may assume that the wavefunction is constant in this
range, so the probability is Ψ2δx.

ANS: The wavefunetions are

The required probability is

E7D.11(b) Calculate the probability that a particle will be found between 0.65L and 0.67L in a
box of length L for the case where the wavefunction is (i) Ψ1 (ii) Ψ2. You may make the same
approximation as in Exercise E7D.11(a).
ANS:

The probability is

where ∆x = 0.02L and the function is evaluated at x = 0.66L.

(a) For n = 1,

(b) For n = 2,

E7D.12(a) For a particle in a box of length L sketch the wavefunction corresponding to the state
with the lowest energy and on the same graph sketch the corresponding probability density.
Without evaluating any integrals, explain why the expectation value of x is equal to L/2.
*
ψn ψn ψn
ANS: For n = 1, the graphs for and will be

The probability of finding particle largest in the middle of box is ∫ ψ n¿ ψ n dx

The value of <x> for a particle in any of the eigenstates of a one-dimensional box is
2 a  nx  a
x     x sin 2  dx x  
n
a 0  a   2
For all values of the the principal quantum number n, which is reasonable. The value of <x2> in
the nth eigenstate is
2
 2 a  n x   a   n2 2 
x2     x 2 sin 2  dx    4  2
 2n   3
n
a 0  a  
 2 a  nx 
x2     x 2 sin 2  dx
an 0
 a 
nx n dy n ay a
y , dy  dx ,  , x , dx  dy
a a dx a n n

 2  a   x  x 1  x cos  2 x  
3 3 3 2
 2  a  
x 2
     y sin  y  dy   
2 2
      sin  2 x   
 a  n   0
 a  n   6  4 8  4 0
 2  a    n  n   a    n 
3 2
1 1 1 
3 2
             a 2   
2 

 a  n   6 4   n   3 2  3 2  n  
2
 a   n 2 2 
x  
2
  4  2 
 2nπ   3 

E7D.12(b) Without evaluating any integrals, state the value of the expectation value of x for a
particle in a box of length L for the case where the wavefunction has n = 2. Explain how you
arrived at your answer.
(Hint: Consider the approach used in Exercise E7D.12(a).)
1 /2
ANS: The wavefunction with n = 2 and is Ψ 2 ( x )= 2
( L ) sin ( 2 πL x ) , which leads to a probability

density P2(x) = |Ψ 2 ( x )| =
2
( 2L ) sin ( 2 πL x )
2
. Graphs of these

functions are shown in Fig

The probability density is symmetric about x = L/2.

Therefore, there is an equal probability of observing
the particle at an arbitrary position x’. and at L – x’.,
so it follows that the average position of the particle
must be at L/2.
E7D.13(a) For a particle in a box of length L sketch the wavefunction corresponding to the state
with n = 1 and on the same graph sketch the corresponding probability density. Without
evaluating any integrals, explain why for this wavefunction the expectation value of x2 is not
equal to (L/2)2?
ANS:

E7D.13(b) For a particle in a box of length L sketch the wave function corresponding to the state
with n = 1 and on the same graph sketch the corresponding probability density. For this
wavefunction, explain whether you would expect the expectation value of x2 to be greater than or
less than the square of the expectation value of x.
1 /2
ANS: The wavefunction with n = 1 and is Ψ 1 ( x ) = 2
( L ) sin ( πLx ) , which leads to a probability

density P1(x) =
2
|Ψ 1 ( x )| =( 2L ) sin ( πLx )
2
. Graphs of these functions are shown in Fig. the average

position of the particle must be at <x> =L/2.

L
2
The expectation value of x2 is found from the integral ∫ x 2|Ψ 1 ( x )| dx
0

Although the probability density will be the same at positions (L/2) −δ and (L/2) +δ, the function
x2 will increase by more between (L/2) and (L/2) +δ, than between (L/2)−δ and (L/2), so in the
2
integral the point at (L/2) +δ has greater weight. It is therefore expected that ⟨ x 2 ⟩ > L .
(2 )
E7D.14(a) An electron is confined to a square well of length L. What would be the length of the
box such that the zero-point energy of the electron is equal to its rest mass energy, mec2? Express
your answer in terms of the parameter λC = h /mec, the 'Compton wavelength' of the electron.
ANS: The zero-point energy is the ground-state energy with n = 1:

( nh )2 h2
E= and E 1 = . Also
8 m e L2 8 m e L2

In terms of the Compton wavelength of an electron.

Set this equal to the rest energy mec2 and solve for L:

So in absolute units, the length L is

E7D.14(b) Repeat Exercise E7D.14(a) for the case of a cubic box of side L.
ANS: The zero-point energy is the ground-state energy, that is, with n1= n2 = n3 = 1:
Set this equal to the rest energy mec2 and solve for L:

where λC = h /mec, is the 'Compton wavelength' of the electron.

E7D.15(a) For a particle in a box of length L and in the state with n = 3, at what positions is the
probability density a maximum? At what positions is the probability density zero?
ANS:

maxima and minima in P (x) correspond to

minima at x = L/6, 3L/6, 5L/6,

Minima at x = L/3, 2L/3
Comment. Maxima in ψ2 correspond to maxima and minima in ψ itself, so one can also solve
this exercise by finding all points where dψ/dx=0.
E7D.15(b) For a particle in a box of length L and in the state with n = 5, at what positions is the
probability density a maximum? At what positions is the probability density a minimum?
ANS:

Maxima and minima in P (x) correspond to

 and

Minima at n’ = 2, 4, 5, 8, so x = 2L/10, 4L/10, 6L/10, 8L/10,

Maxima and minima alternate: maxima correspond to

n’ = 1, 3, 5, 7, 9, ….. so