Chemistry 460

Fall 2017
Dr. Jean M. Standard
September 11, 2017

The Particle in a Half-Infinite Well

Consider a particle in a one-dimensional half-infinite well. The potential is shown in Figure 1.

V=V0

III I II

x=0 x=L
Figure 1. Potential energy for a particle in a half-infinite box in one dimension.

Like the particle in a box, the potential in region III is infinite and in region I equals zero. However, in this case, the
potential in region II is not infinite but rather a finite value ( V0 ). In terms of an equation, the potential energy is
given by

⎧ ∞, x < 0 ⎫
⎪ € ⎪
V (x) = ⎨ 0, 0 ≤ x ≤ L ⎬. (1)
⎪V , x > L ⎪
⎩ 0 ⎭

The method of solution is similar to the particle in a box. The steps are as follows:
1. A general solution to the Schrödinger equation is obtained in each region.
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2. In order for the solution to represent a proper quantum mechanical wavefunction, the solution in each
region where the coordinate goes to ±∞ must be checked to ensure it is finite.
3. The solution is required to be continuous by making sure that the solutions in each of the regions match at
the boundaries. At boundaries that do not involve an infinite potential, we also must require continuity of
the first derivative of the wavefunction.
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4. Restrictions on the allowed energies are obtained from the matching conditions.
5. Finally, the wavefunction must be properly normalized.

1. General Solutions
Region III Solution
The Schrödinger equation in Region III is

⎧ !2 d 2 ⎫
⎨− 2
+ ∞ ⎬ ψ III ( x ) = E ψ III ( x ) . (2)
⎩ 2m dx ⎭

This is the same Schrödinger equation that we saw for outside region of the particle in a box. We showed
previously that the solution for this was a wavefunction that was zero in the region. To review this solution, first
€
move the constant ( ∞ ) term to the right side,

!2 d 2
− ψ III ( x ) = ( E − ∞ ) ψ III ( x) . (3)
€ 2m dx 2

€
 2

Then, since E − ∞ equals −∞ , the right side of the equation can be simplified,

!2 d 2
− ψ III ( x ) = − ∞ ψ III ( x ) . (4)
€ € 2m dx 2

Finally, the minus sign can be eliminated and both sides can be divided by the constant ( ∞ ).
€
1 ⎧ !2 d 2 ⎫
⎨ 2
ψ III ( x) ⎬ = ψ III ( x) . (5)
∞ ⎩ 2m dx ⎭ €

Since 1/ ∞ is zero, the whole left side goes to zero and we get for the wavefunction in region III the solution

€
ψ III ( x) = 0 . (6)
€

Region I Solution
The Schrödinger equation in Region I€is

⎧ !2 d 2 ⎫
⎨− 2
+ 0 ⎬ ψ I ( x) = E ψ I ( x) . (7)
⎩ 2m dx ⎭

This is the same Schrödinger equation that we saw for the inside region of the particle in a box. We showed
previously that the general solution may be written in the form of either trigonometric functions (sines/cosines) or
€
exponentials. It is most convenient in the case that the particle is in a classically bound region to use the
trigonometric form, while if the particle is in a classically unbound region the exponentials are more convenient. In
this example, we will consider particle energies such that E < V0 , so trig functions are appropriate. The general
solution in region I is therefore given by

ψ I ( x) = A sin kx + B cos kx , (8)

€
where A, B, and k are arbitrary constants.
€ by substitution of the general form into the Schrödinger equation,
The constant k may be determined

!2 d 2 (9)
− ψ I ( x ) = E ψ I ( x) .
2m dx 2

Substituting,
€
!2 d 2
− { A sin kx + B cos kx} = E { A sin kx + B cos kx} . (10)
2m dx 2

Taking the second derivative on the left and simplifying yields

€
!2
− −Ak 2 sin kx − Bk 2 cos kx
{ } = E { A sin kx + B cos kx} (11)
2m

! 2k 2
{ A sin kx + B cos kx} = E { A sin kx + B cos kx} .
2m

€
 3

Since the function in the brackets is the same on both sides, we can divide this out to give

! 2k 2 (12)
= E.
2m

Solving for the constant k,

€
2mE (13)
k = .
!

So the wavefunction ψ I ( x ) = A sin kx + B cos kx is a solution of the Schrödinger equation if k is related to the
energy by the expression given above.
€

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Region II Solution
The Schrödinger equation in Region II is

⎧ !2 d 2 ⎫
⎨− 2
+ V0 ⎬ ψ II ( x ) = E ψ II ( x ) . (14)
⎩ 2m dx ⎭

Collecting terms involving constants and multiplying through to isolate the second derivative on the left, the
equation can be rewritten as
€
d2 2m (V0 − E)
(15)
2
ψ II ( x) = ψ II ( x) .
dx !2

This equation is similar to that for region I, except that the constant term multiplying the wavefunction on the right
involves V0 − E instead of just E. Therefore, the general solution can be written in the form of either trigonometric
€
functions (sines/cosines) or exponentials. Since we are considering particles for which E < V0 , region II is a
classically forbidden region; therefore, the exponential solution is most appropriate.
€
The general solution in region II can be written
€
ψ II ( x ) = C e λx + De − λx , (16)

where C and D are arbitrary constants and λ is a real, positive constant. Note that in this expression, a different
exponent rather than k is employed. In the solution for region I, a specific relationship between k and E was
€
established; therefore, the same constant cannot be used in region II.
€
We must establish the relationship between λ and E in region II by substitution of the general solution into the
Schrödinger equation,

⎧ !2 d 2 ⎫
⎨ − € 2 + V0 ⎬ ψ II ( x ) = E ψ II ( x ) , (17)
⎩ 2m dx ⎭
⎧ ! d
2 2 ⎫
⎨−
⎩ 2m dx
2 ( ) (
+ V0 ⎬ C e λx + De − λx = E C e λx + De − λx .
⎭
)

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 4

Moving the constant terms multiplying the wavefunction to the right, taking the second derivative, and simplying
yields

!2
−
2m
(
C λ2 e λx + D λ2e− λx ) ( )
= ( E − V0 ) C e λx + De− λx , (18)

! 2 λ2
−
2m
(
C e λx + D e− λx ) ( )
= ( E − V0 ) C e λx + De− λx .

Since the function in the parentheses is the same on both sides, we can divide this out to give
€
! 2 λ2 (19)
− = E − V0 .
2m

Solving for the constant λ ,

€
2m (V0 − E)
λ = . (20)
€ !

Thus we see that this constant has a different relationship to the energy than the constant k defined for region I.
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Summary of Solutions
To summarize, the general solutions that we have found so far in the three regions are

⎧ 0, x < 0 ⎫
⎪ ⎪
ψ (x) = ⎨ A sin kx + B cos kx, 0 ≤ x ≤ L ⎬. (21)
⎪ C e λx + D e− λx , x > L ⎪
⎩ ⎭

2. Conditions at Infinity
€ must be finite, it must be tested to ensure that it does not blow up as x → ± ∞. This
Because the wavefunction
condition may affect the solution in regions III and II.

In region III, since the wavefunction is zero everywhere, it is already finite as x → − ∞; therefore, no adjustments
€
have to be made to the solution in region III.

In region II, the general solution is

€
ψ II ( x ) = C e λx + De − λx . (22)

λx
In this case, region II encompasses the coordinate range as x → ∞ . The first term C e blows up as x → ∞ and
makes the wavefunction in this region
€ blow up. The only way around this is to set C = 0. Thus, the solution in
region II must be reduced to the form
€ € €
ψ II ( x ) = De − λx . (23)

€
 5

3. Continuity at the Boundaries

A proper quantum mechanical wavefunction must be continuous, so the continuity at the boundaries between the
regions must be checked. In addition, for regions that do not involve infinite potentials, the first derivative of the
wavefunction also must be continuous.

Matching at x=0
Since the potential is infinite in region III, only the wavefunction must be continuous across the boundary between
regions III and I. The criterion for matching the wavefunction between regions III and I is

ψ III ( 0) = ψ I ( 0) . (24)

Substituting the general solutions for the wavefunctions in regions III and I gives
€ (25)
0 = A sin 0 + B cos 0
0 = 0 + B
0 = B.

The continuity requirement leads to the elimination of one of the terms in the general solution of region I. Thus, we
are left with
€
ψ I ( x) = A sin kx . (26)

Matching at x=L
€ II; thus, both the wavefunction and its first derivative must be continuous
The potential is finite in regions I and
across the boundary. The equations that specify continuity at x=L are

ψ I ( L) = ψ II ( L ) (27)
ψʹI ( L) = ψʹII ( L ) .

It is convenient mathematically to use the ratio of these equations,

€
ψʹI ( L) ψʹII ( L ) (28)
= .
ψ I ( L) ψ II ( L )

The first derivatives of the wavefunctions in regions I and II are

€
ψʹI ( x ) = Ak cos kx (29)
− λx
ψʹII ( x ) = − Dλ e .

Taking the ratio of the continuity equations and substituting yields

€
ψʹI ( L) ψʹII ( L )
= (30)
ψ I ( L) ψ II ( L )
or
Ak cos kL −D λ e − λL
= .
A sin kL D e − λL

This procedure allows cancellation of the arbitrary constants A and D. Upon simplification, the equation becomes
€ (31)
k cot kL = − λ .

€
 6

4. Quantization of Energy
It can be shown that the matching condition leads to quantization of the energy levels. First, recall that

2mE 2m(V0 − E)
k = and λ = . (32)
! !

Substituting these relations into the matching condition yields

€ k cot kL = − λ
or

2mE ⎧ 2mE ⎫ 2m(V0 − E)

cot ⎨ L⎬ = − . (33)
! ⎩ ! ⎭ !

In this equation, m, ! , L and V0 are all constants. Therefore, this equation is of the form
€
f ( E) = g ( E) . (34)
€ €
where f and g are functions of E. Solutions to this equation exist only for specific values of E; thus, E is quantized
in this system. Note that because the equation is transcendental, the matching condition cannot be solved
€
analytically for E. However, the quantized E values may be obtained either graphically or numerically.

Graphical Solution
To obtain the quantization condition in a more useful form for the graphical solution, start with the definition of λ ,

2m(V0 − E) 2m(V0 − E)
λ = , or λ2 = . (35)
! !2 €

Distributing the terms yields

€ 2mV0 2mE
λ2 = 2
− . (36)
! !2

However, since we know that from the definition of k that

€
2mE 2mE
k = or k 2 = , (37)
! !2

2
we can substitute for the last term in the expression for λ to get
€
1/ 2
2 2mV0 2 ⎡ 2mV0 2⎤
λ = − k or λ = ⎢ 2 − k ⎥ . (38)
! 2€ ⎣ ! ⎦

The quantization condition found above is

€ (39)
k cot kL = − λ .

€
 7

Multiplying both sides by L and substituting the definition of λ gives

k L cot kL = − λ L
€ ⎡ 2mV ⎤1/ 2
k L cot kL = − ⎢ 2 0 − k 2 ⎥ L
⎣ ! ⎦
⎡ 2mV L2 2
⎤1/ 2
0 (40)
k L cot kL = − ⎢ − ( ) ⎥ .
k L
⎢⎣ ! 2 ⎥⎦

Now, for the sake of ease in graphing, define a new unitless variable z such that
€ (41)
z = k L.

Note that since k is directly related to square root of the energy E, z is also directly related to the square root of
energy. The equation now may be expressed in terms of the variable z. Also, define a new unitless constant α
€
such that

⎛ 2mV L2 ⎞1/ 2
α = ⎜⎜ 0 ⎟⎟ . € (42)
2
⎝ ! ⎠

Starting with the quantization condition and substituting yields

€
⎡ 2mV L2 2
⎤1/ 2
k L cot kL = − ⎢ 0 − ( k L) ⎥ (43)
⎢⎣ ! 2 ⎥⎦

1/ 2

€
[
z cot z = − α 2 − z 2 ] . (44)

1/ 2
[
Let f ( z ) = z cot z and g( z ) = − α 2 − z 2
€
] . The equation is satisfied only for specific values of z for which
f ( z ) = g ( z ) . To obtain the solutions graphically, we plot f ( z ) vs. z and g( z ) vs. z and look for intersections.
The solution shown in Figure 2 is for α = 6.0 . If a different value of α is used, then the intersection points will be
€ different. €
€ € €
€

Figure 2. Graphical solution of particle in a half-infinite well for α=6.0.

 8

Note that for this specific case, there are two intersection points; thus, there are two quantized energies for this case
for the particle in a half-infinite well. From the graphical solution, these intersection points occur at values of z of
approximately 2.7 and 5.2.

To convert these values of z back into energies, recall the definition of z,

z = k L. (45)

Substituting the expression relating k and E,

€
2mE 2mE L2
z = L or z 2 = . (46)
! !2

We can now solve for E to get

€
! 2z 2
E = . (47)
2 m L2

Interestingly, this result is similar to the result that we obtained for the particle in an infinite one-dimensional box,
€
! 2n 2π 2
E = , (48)
2 m L2

where in the particle in an infinite box we have n π instead of z.

€
To obtain numerical values of the energies for the particle in a half-infinite box, we have to specify values for m and
L.
€

5. Determination of Wavefunction
So far, the wavefunction for the system is given by

⎧ 0 x < 0 ⎫
⎪ ⎪
ψ (x) = ⎨ A sin kx 0 ≤ x ≤ L ⎬. (49)
⎪ D e− λx x > L ⎪
⎩ ⎭

The two constants A and D are still unknown. To find D, we can use the boundary condition at x=L for the
continuity of the wavefunction, ψ I ( L) = ψ II ( L ) ,
€

A sin kL = De− λL . (50)

€
Solving for D yields
€
D = A e λL sin kL . (51)

Substituting this into the expression for the wavefunction gives

€ ⎧ ⎫
⎪⎪ 0 x < 0 ⎪⎪
ψ (x) = ⎨ A sin kx 0 ≤ x ≤ L ⎬. (52)
⎪ ⎪
( λL
⎪⎩ A e sin kL e )− λx x > L ⎪⎭

€
 9

In the expression for the wavefunction, the constant A is still arbitrary. It can be determined by requiring the
wavefunction to be normalized,

∞
∫ ψ *( x) ψ( x) dx = 1. (53)
−∞

Substituting,

L € ∞
2 2 2 2 λL 2
A ∫ sin kx dx + A e sin kL ∫ e−2λx dx = 1. (54)
0 L

Evaluating the integrals and solving for A yields

€
⎡L 1 1 ⎤−1/ 2
A = ⎢ − sin 2kL + sin 2 kL ⎥ . (55)
⎣2 4k 2λ ⎦

This completes the solution. For the specific case with α = 6.0 , L=3.0 bohr, and V0 = 2.0 hartrees, the two
wavefunctions are shown in Figure 3.
€
0.8
€ 0.8
€
0.7
0.6

0.6
0.4

0.5
0.2
ψ1(x)

0.4
ψ2(x)

0.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
0.3
-0.2

0.2
-0.4

0.1
-0.6

0.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 -0.8
x (bohr) x (bohr)

(a) (b)
Figure 3. (a) Ground and (b) first excited state wavefunctions for the particle in a half-infinite well.

The dashed line at x=3.0 bohr (or x=L) indicates the position of the finite potential well. In both cases, the
wavefunction extends beyond x=L even though the energy of the particle is less than the value of the potential well.
For a classical particle with E < V0 , there is no way for it penetrate into the region where x > L; this region is called
the classically forbidden region. In quantum mechanics, however, we see that the wavefunction is nonzero in this
region; therefore, there is a finite probability that the quantum mechanical particle will be found in the classically
forbidden region. This penetration of the wavefunction into a classically forbidden region is referred to as quantum
€
mechanical tunneling.