Radial Wave Functions from the Solution of the Radial

Equation
Again per example 10–6, the solutions of the radial equation are equation (10–15),

yjk (x) = e−x/2 x(k+1)/2 Lkj (x).

Since

k = 2l + 1, (k + 1)/2 = ((2l + 1) + 1)/2 = l + 1, and j + l + 1 = n ⇒ j = n − l − 1,

we can now express the indices in terms of the quantum numbers n and l, meaning

ynl (x) = e−x/2 xl+1 L2l+1

n−l−1 (x),

so the solution starts to assume some of the traits of the hydrogen atom. The independent variable
is still x = ²r. We need an independent variable r, or at least in terms of r, to be consistent
with the spherical coordinate system. Using (10–20) and (10–27), we can solve for ² in terms of
the Bohr radius and the principal quantum number,
³ ² ´2 µ ¶
2µE 2µ h̄2 1
=− 2 =− 2 − =
2 h̄ h̄ 2µa20 n2 a20 n2

4 2
⇒ ²2 = ⇒ ²= ,
a20 n2 a0 n
2r
⇒ x= ,
na0
and this is in terms of the desired independent variable, or
µ ¶l+1 µ ¶
2r 2r
ynl (r) =e −r/na0
L2l+1
n−l−1 .
na0 na0

Finally we can relate the associated Laguerre function to the radial function we set out to find
through equation (10–19). Remember y(r) = r R(r), so
µ ¶l+1 µ ¶
2r 2r
r Rn,l (r) = e −r/na0
L2l+1
n−l−1
na0 na0
µ ¶l µ ¶
2r 2r
⇒ Rn,l (r) = A e−r/na0 L2l+1
n−l−1 ,
na0 na0
where we have added a normalization constant which has absorbed the factor 2/na0 from the
power term when we cancel the factor of r. This still needs to be normalized. We want the radial
functions to be individually normalized so the product of the radial wave functions and spherical
harmonics, the hydrogen wave function, is normalized. The normalized radial wave functions are
v
uµ ¶ µ ¶l µ ¶
u 2 3 (n − l − 1)! −r/na 2r 2r
Rn,l (r) = t £ ¤3 e 0 2l+1
Ln−l−1 . (10 − 28)
na0 2n (n + l)! na0 na0

347
 The first few normalized radial wave functions are listed in table 10–5.
−3/2 −r/a0
R1,0 (r) = 2a0 e
µ ¶
1 −3/2 r
R2,0 (r) = √ a0 1− e−r/2a0
2 2a0
1 r −r/2a0
R2,1 (r) = √ a−3/2
0 e
24 a0
µ ¶
2 −3/2 2r 2r2
R3,0 (r) = √ a0 1− + 2 e−r/3a0
27 3a 0 27a 0
µ ¶
8 −3/2 r r
R3,1 (r) = √ a0 1− e−r/3a0
27 6 6a0 a0
4 r2 −r/3a0
R3,2 (r) = √ a−3/2
0 e
81 30 a20
Table 10 − 5. The First Six Radial Wave Functions for Hydrogen.

Example 10–10: Show equation (10–28) is properly normalized.

We want to normalize
µ ¶l µ ¶
2r 2r
Rn,l (r) = A e−r/na0 L2l+1
n−l−1 .
na0 na0
The normalization condition for a function of the radial variable in spherical coordinates is
Z ∞³ ´∗
¯
< ψ(r)¯ψ(r)> = 1 = Rn,l (r) Rn,l (r) r2 dr
0

where the factor of r2 is the radial portion of the volume element in spherical coordinates. Using
the radial wave functions, this is
Z ∞à µ ¶l µ ¶!∗ µ ¶l µ ¶
−r/na0 2r 2l+1 2r −r/na0 2r 2l+1 2r
1= Ae Ln−l−1 Ae Ln−l−1 r2 dr
0 na0 na0 na0 na0
Z ∞ µ ¶2l µ ¶ µ ¶
∗ −2r/na0 2r ¡ 2 ¢ 2l+1 2r 2l+1 2r
= A A,e r Ln−l−1 Ln−l−1 dr
0 na0 na0 na0
Z µ ¶2l+2 µ ¶ µ ¶ µ ¶
¯ ¯2 ³ na0 ´3 ∞ −2r/na 2r 2r 2r 2r
= ¯A¯ e 0
L2l+1
n−l−1 L 2l+1
n−l−1 d (10
, − 29)
2 0 na0 na0 na0 na0
where the cubic factor preceding the integral comes from the fact we have grouped the factor of
r2 with the other powers of r, and also have expressed the differential in terms of the argument
of the associated Laguerre polynomial. We are going to borrow two relations from Morse and
Feshbach7 , the first of which is
Z ∞ 3
[ Γ(a + b + 1)]
z a e−z Lab (z) Lab (z) dz = δb,c . (10 − 30)
0 Γ(b + 1)
7
Morse and Feshbach, Methods of Theoretical Physics (McGraw–Hill, New York, 1953), pp.
784–785

348
There are some things to notice about equation (10–30). The Kronecker delta δb,c reflects
the orthogonality of the associated Laguerre polynomials. The integral is zero unless the lower
indices of the two associated Laguerre polynomials are identical. Also, we expect all indices to be
integers, so expect the gamma functions to become factorials. Comparing (10–29) and (10–30), the
argument of the associated Laguerre polynomial, the base of the power term, and the differential
are all the same in both equations. The upper index of the associated Laguerre polynomials and
the power term are the same in (10–30), but differ in (10–29). We can adjust (10-29) using a
recursion relation from Morse and Feshbach,
¡ ¢ b+1 ¡ ¢2
z Lab (z) = a + 2b + 1 Lab (z) − Lab+1 (z) − a + b Lab−1 (z).
a+b+1
If we take one factor of the power term and group it with the first associated Laguerre polynomial,
we get
Z µ ¶2l+1 ½µ ¶ µ ¶¾ µ ¶ µ ¶
¯ ¯2 ³ na0 ´3 ∞ −2r/na 2r 2r 2r 2r 2r
1= A¯ ¯ e 0 2l+1
Ln−l−1 2l+1
Ln−l−1 d ,
2 0 na0 na0 na0 na0 na0
which makes the exponent of the power term match the upper index of the associated Laguerre
polynomial, and we can evaluate the term in braces using the recursion relation. For a = 2l + 1
and b = c = n − l − 1, this is
µ ¶ µ ¶ µ ¶
2r 2l+1 2r ¡ ¢ 2l+1 2r
Ln−l−1 = 2l + 1 + 2n − 2l − 2 + 1 Ln−l−1
na0 na0 na0
µ ¶ µ ¶
n−l−1+1 2l+1 2r ¡ ¢2 2l+1 2r
− L − 2l+1+n−l−1 Ln−l−2
2l + 1 + n − l − 1 + 1 n−l na0 na0
µ ¶ µ ¶ µ ¶
2l+1 2r n−l 2l+1 2r ¡ ¢2 2l+1 2r
= 2n Ln−l−1 − L − n + l Ln−l−2 .
na0 n + l + 1 n−l na0 na0
We are going to ignore all but the first term. We could substitute all three terms into the integral,
distribute other factors, break the integral into three integrals, and evaluate each one using equa-
tion (10–30). But the Kronecker delta tells us integrals with unequal lower associated Laguerre
polynomial indices will be zero. The only non–vanishing integral will come from the first term, so
Z µ ¶2l+1 ½ µ ¶¾ µ ¶ µ ¶
¯ ¯2 ³ na0 ´3 ∞ −2r/na 2r 2r 2r 2r
1= A¯ ¯ e 0 2l+1
2n Ln−l−1 2l+1
Ln−l−1 d ,
2 0 na0 na0 na0 na0
Z µ ¶2l+1 µ ¶ µ ¶ µ ¶
¯ ¯2 ³ na0 ´3 ∞ −2r/na 2r 2r 2r 2r
¯
= A 2n ¯ e 0 2l+1
Ln−l−1 2l+1
Ln−l−1 d ,
2 0 na0 na0 na0 na0
and we are ready to evaluate this integral using equation (10–30) where
µ ¶
2r
z → , a → 2l + 1, b = c → n − l − 1,
na0
and for integers Γ(j) = (j − 1)!. Then
¯ ¯2 ³ na0 ´3 3
[Γ (2l + 1 + n − l − 1 + 1)]
1 = ¯ A ¯ 2n
2 Γ(n − l − 1 + 1)
¯ ¯2 ³ na0 ´3 [Γ (n + l + 1)]
3
= ¯ A ¯ 2n
2 Γ(n − l)
¯ ¯2 ³ na0 ´3
3
[(n + l)!]
= ¯ A ¯ 2n
2 (n − l − 1)!

349
 v
uµ ¶
u 2 3 (n − l − 1)!
⇒ A=t £ ¤3
na0 2n (n + l)!

v
uµ ¶ µ ¶l µ ¶
u 2 3 (n − l − 1)! −r/na 2r 2r
⇒ Rn,l (r) = t £ ¤3 e 0 2l+1
Ln−l−1 .
na0 2n (n + l)! na0 na0

Example 10–11: Calculate R3,1 (r) from equation (10–29).

For n = 3, l = 1,

v
uµ ¶ µ ¶1 µ ¶
u 2 3 (3 − 1 − 1)! −r/3a 2r 2r
R3,1 (r) = t £ ¤3 e 0 2(1)+1
L3−1−1
3a0 2(3) (3 + 1)! 3a0 3a0
sµ ¶ µ ¶ µ ¶
2 23 1 −r/3a0 r 3 2r
= £ ¤ e L1
3 33 a30 2 · 3 (4 · 3 · 2) 3 a0 3a0
s µ ¶µ µ ¶ ¶
2 22 −3/2 −r/3a0 r 2r
= £ ¤a e −24 + 96
3 34 26 · 33 · 23 0 a0 3a0
r µ µ ¶ ¶
2 22 −3/2 r r −r/3a0
= 96 a − + 1 e ,
3 29 · 37 0 6a0 a0

and because 96 = 25 · 3,

r µ ¶
26 1 −3/2 r r −r/3a0
R3,1 (r) = 3 3 a0 1− e
2 ·3 2·3 6a0 a0
µ ¶
8 −3/2 r r −r/3a0
= √ a0 1− e ,
27 6 6a0 a0

in agreement with table 10–5.

Graphs of Radial Wave Functions

The radial wave functions listed in table 10–5 are plotted in figure 10–1. The radial wave
functions are all individually normalized, so the probability associated with radial wave functions
is
Z ∞ Z ∞
¯ ¯
¯ ¯
< ψ(r) ψ(r)> = < Rn,l (r) Rn,l (r)> = ∗ 2
Rn,l (r) Rn,l (r) r dr = R2n,l (r) r2 dr,
0 0

where the factor of r2 in the integrals is from the volume element in spherical coordinates.
The functions R2n,l (r) r2 are the radial probability densities for the hydrogen atom. The radial
probability densities are plotted abreast their corresponding radial wave function in figure 10–2.

350
 Figure 10 − 1. Radial Wave Functions. Figure 10 − 2. Radial Probability Densities.

Hydrogen Wave Functions

We have all three parts. The product of the azimuthal, polar, and radial wave functions are
the hydrogen wave functions. The product of the azimuthal and polar wave functions are the
spherical harmonics, so the hydrogen wave functions are the product of the radial wave functions
and spherical harmonics,
ψnlm (r, θ, φ) = Rn,l (r)Yl,m (θ, φ).
You can construct the desired hydrogen wave function by selecting the appropriate radial wave
function from table 10–5, or calculating it from equation 10–28, and multiplying it by the appro-
priate spherical harmonic from table 11–1, or calculating it from equation 10–10, i.e.,

ψnlm (r, θ, φ) = Rn,l (r)Yl,m (θ, φ).

The equation ¯
< r, θ, φ¯n, l, m> = Rn,l (r)Yl,m (θ, φ)
denotes representation from Hilbert space.

Example 10–10: What is ψ3,1,−1 (r, θ, φ)?

From tables 10–5 and 11–1,
µ ¶ r
8 −3/2 r r −r/3a0 3
R3,1 (r) = √ a0 1− e , Y1,−1 (θ, φ) = sin θ e−iφ ,
27 6 6a0 a0 8π
so
ψ3,1,−1 (r, θ, φ) = R3,1 (r) Y1,−1 (θ, φ)
µ ¶ r
8 −3/2 r r −r/3a0 3
= √ a0 1− e sin θ e−iφ
27 6 6a 0 a 0 8π
√ µ ¶
8 3 −3/2 r r −r/3a0
= √ √ a0 1− e sin θ e−iφ
27 6 8π 6a 0 a 0
µ ¶
2 −3/2 r r
= √ a0 1− sin θ e−r/3a0 −iφ .
27 π 6a0 a0

Graphics of Hydrogen Wave Functions

The probability of finding the electron in a hydrogen atom in a specific volume is
Z Z Z Z
¯ ¯ r2 θ2 φ2 ¯ ¯
¯ψnlm (r, θ, φ)¯2 dV = ¯ψnlm (r, θ, φ)¯2 r2 sin θ dr dθ dφ.
∆V r1 θ1 φ1

The probability of finding the electron of the hydrogen atom anywhere in space is non–zero, how-
ever, the probability is vanishingly small for most locations. The locations where the probability
densities are highest are depicted in figure 10–3.

351
 Figure 10 − 3. Graphics for Significant Probability Densities by Quantum Number.
The graphics of figure 10–3 are illustrative and are a culmination of the calculations of this chapter.
Additional calculations demonstrate the similarity of simpler systems to this realistic system. In
many regards, the techniques developed earlier with simpler systems were examined so we could
arrive at the hydrogen atom and figure 10–3.

Quantum Numbers and Chemistry Terminology

Another depiction explains common chemistry terminology in terms of quantum numbers.
The ground state of hydrogen is n = 1, l = 0 and m = 0. Common chemistry designations
for the ground state are the K–shell and the 1s subshell. Remember the K–shell may house two
electrons in many electron atoms. This means the one electron in the hydrogen atom can exist
in one of two possible states, though there is only one possible combination of the three quantum
numbers n, l, and m. There is, however, a fourth quantum number associated with spin.
For each set of the three quantum numbers n, l, m, there is a possibility of spin up or spin
down, and thus two possible states associated with the quantum numbers n = 1, l = 0, and
m = 0, therefore two states associated with the K–shell. We will examine spin in the next chapter.
The point of the moment is the desigation K–shell and quantum number n = 1 have the same
meaning. The quantum number n = 2 is the same as the chemical designation of L–shell. The
L–shell has subshells 2s and 2p, where s corresponds to l = 0 and p corresponds to l = 1,
which are possible quantum numbers for n = 2. For l = 1, m = −1, 0, or 1 so there are three
states possible in the p subshell. Each of the four L–shell states may have spin up or spin down,
so there are eight possible eigenstates in the L–shell. The M–shell corresponds to n = 3, the
N–shell corresponds to n = 4, and the O–shell corresponds to n = 5. As the quantum number
n becomes larger, the quantum number l can take on a greater range of values. The quantum
number l = 0 corresponds to the s–subshell, the quantum number l = 1 corresponds to the
p–subshell, the quantum number l = 2 corresponds to the d–subshell, the quantum number l = 3
corresponds to the f –subshell, and the quantum number l = 4 corresponds to the g–subshell.
Each subshell has 2l + 1 states. The total states in each shell is n2 . Figure 10–4 summarizes
the commentary in this discussion.

total
shell n2
O n=5 5s 1 5p 3
5d 5 5f 7
5g 9
25
N n=4 4s 1 4p 3
4d 5 4f 7
16
↑ M n=3 3s 1 3p 3
3d 5 9
E L n=2 2s 1 2p 3
4
K n=1 1s 1 1
l=1 l=2 l=3 l=4 l=5

Figure 10 − 4. Quantum Number, Chemical Designation Correspondence.

The subscripts on the underbars of the subshells indicate the number
of states 2l + 1 in that subshell.

One final comment. Since the energy, to this point, depends only on n, the quantum numbers
l and m having no effect on energy, we have an n2 –fold degeneracy in energy using this picture.

352
A magnetic field removes this degeneracy...the same magnetic field that will define the z-axis
and provide orientation to the scheme, will remove this degeneracy. This was explored by Pieter
Zeeman, so is known as the Zeeman effect. Pragmatically, a field is necessary if the orientation is
to make sense.
Possibilities and Probabilities
In addition to being of intrinsic interest because it is a real system, the electron in a hydrogen
atom is a particle in a fancy box. Comparable to a particle in the infinite square well or harmonic
oscillator, the electron is confined. Also comparable to other systems, the state vector describing
the electron in a hydrogen atom is a linear combination of eigenstates. We assume a limited linear
combination to provide some sample calculations which should be reminiscent of calculations for
other systems. The examples in that follow all refer to the t = 0 state vector

Ψ(r, θ, φ) = 2ψ1,0,0 + ψ2,1,0 (10 − 31)

Example 10–13: Normalize equation (10–31).

The state function is composed of 2 parts ground state and 1 part of the given excited state,
so we can write µ ¶ µ ¶ µ ¶
1 0 2
Ψ(r, θ, φ) = 2 + = ,
0 1 1
so the normalization condition can be written
µ ¶
¡ ¢ 2 ¯ ¯2 ¡ ¢
∗
1 = A 2, 1 A = ¯A¯ 4 + 1
1
1
⇒ A= √
5
2 1
⇒ Ψ(r, θ, φ) = √ ψ1,0,0 + √ ψ2,1,0
5 5
is the properly normalized wave function or state vector.

Example 10–14: Normalize equation (10–31) using the orthonormality of the spherical har-
monics.
This example demonstrates a useful technique using spherical harmonics as well as the reason
the radial wave functions are individually normalized.

Ψ(r, θ, φ) = 2ψ1,0,0 + ψ2,1,0

= 2 R1,0 Y0,0 + R2,1 Y1,0 ,

and the normalization condition is

Z
¡ ¢ ¡ ¢
1= A∗ 2 R1,0 Y0,0 + R2,1 Y1,0 A 2 R1,0 Y0,0 + R2,1 Y1,0 dV
V
Z
¯ ¯2 ¡ 2 2 ¢
= A¯ ¯ 4 R1,0 Y0,0 + 4R2,1 R1,0 Y1,0 R1,0 Y0,0 + R22,1 Y1,0
2
dV
V
µZ Z Z ¶
¯ ¯2
= ¯A¯ 2 2
4 R1,0 Y0,0 dV + 4R2,1 R1,0 Y1,0 Y0,0 dV + 2 2
R2,1 Y1,0 dV
V V V

353
 µ Z Z Z Z Z Z ¶
¯ ¯2 ∞ ∞ ∞
¯
= A ¯ 4 R21,0 r2 dr 2
Y0,0 dΩ + 4 2
R2,1 R1,0 r dr Y1,0 Y0,0 dΩ + R22,1 r2 dr 2
Y1,0 dΩ
0 Ω 0 Ω 0 Ω
µ Z ∞ ¶
¯ ¯2 ¡ ¢¡ ¢ ¡ ¢ ¡ ¢¡ ¢
= ¯A¯ 4 1 1 + 4 2
R2,1 R1,0 r dr 0 + 1 1 (10 − 32)
0
R
where Y1,0 Y0,0 dΩ is zero because the spherical harmonics are orthonormal, so

¯ ¯2 ¡ ¢ 1
1 = ¯A¯ 4 + 0 + 1 ⇒ A = √
5

2 1
⇒ Ψ(r, θ, φ) = √ ψ1,0,0 + √ ψ2,1,0 .
5 5

The orthonormality of spherical harmonics means

Z
Yi,j Yk,l dΩ = δi,k δj,l ,

We have previously done this calculation using < i|j> = δi,j , which is the same statement for
systems in a Hilbert space. If integrated over solid angle, the indices must be identical or the
integral is zero, as illustrated in equation (10–32). The radial wave functions are not orthonormal,
but they are normalized. This means
Z ∞
Ri,j Ri,j r2 dr = 1.
0

Note the matching indices. If the indices match, the integral of their product and r2 over all
possible values of radius is 1. If the indices do not match, you will often have the good fortune
of a multiplication by zero by virtue of the integral of the spherical harmonics as in equation
(10–32). In the circumstance the spherical harmonics are the same, the integral of radial functions
will vanish. The bottom line is the hydrogen wave functions are orthonormal. The radial wave
functions themselves, however, are normalized but they are not orthonormal.
A third method to calculate the normalization constant is to use the representations of the
hydrogen wave functions and do the integrations explicitly. That method is much longer and more
difficult than either of the previous two examples, and will yield the same result.

Example 10–15: What are the possible results of individual measurements of energy, angular
momentum, and the z–component of angular momentum?
The possible results are the eigenvalues. For

2 1
Ψ(r, θ, φ) = √ ψ1,0,0 + √ ψ2,1,0
5 5

we could measure a state with a principal quantum number of n = 1 or n = 2. The corresponding

eigenenergies are

13.6 eV 13.6 eV
En = − ⇒ E1 = −13.6 eV, or − = −3.4 eV
n2 4
354
so are the possible results of a measurement of energy. For a measurement of angular momentum,
we could measure a state with orbital angular momentum quantum number of l = 0 or l = 1,
so anticipate a measurement of
p p √
0(0 + 1)h̄ = 0 or 1(1 + 1)h̄ = 2h̄

because the eigenvalues of the square of angular momentum, L2 , are l(l + 1)h̄. The eigenvalues
of the z–component of angular momentum are mh̄, and both eigenstates of the state vector have
m = 0, so the only possibility of a measurement of the z–component of angular momentum is
0 h̄ = 0.

Example 10–16: What are the probabilites of the possible results of individual measurements
of energy, angular momentum, and the z–component of angular momentum?
¯ ¯ ¯2
The probabilites are ¯ < ψ ¯Ψ> ¯ , so the probability of measuring E0 = −13.6 eV , cor-
responding to measuring the eigenstate with n = 1, and the probability of measuring orbital
angular momentum of 0, corresponding to measuring the eigenstate with l = 0, is
¯ ¯ ¯2
¡ ¢¡√ ¢ ¯ ¯ 2 1 ¯
P E = −13.6 eV = P L = 0 = ¯< ψ1,0,0 ¯ √ ψ1,0,0 + √ ψ2,1,0>¯¯
2 ¯ ¯
5 5
¯ ¯2
¯ 2 ¯ 1 ¯ ¯
= ¯¯ √ < ψ1,0,0 ¯ψ1,0,0> + √ < ψ1,0,0 ¯ψ2,1,0>¯¯
5 5
¯ ¯2
¯ 2 ¡ ¢ ¯ 4
= ¯¯ √ 1 + 0¯¯ =
5 5

where we have used the orthonorality of eigenstates, regardless of whether we represent the eigen-
states as functions of position and use the orthonormality of the spherical harmonics, or use a
more general argument like < i|j> = δij . Similarly, the probability of measuring E1 = −3.4 eV ,
corresponding to measurement√of the eigenstate with n = 2, and the probability of measuring
orbital angular momentum of 2h̄, corresponding to measuring the eigenstate with l = 1, is
¯ ¯ ¯2
¡ ¢ ¡√ √ ¢ ¯ ¯ 2 1 ¯
P E = −3.4 eV = P L = 2h̄ = ¯< ψ2,1,0 ¯ √ ψ1,0,0 + √ ψ2,1,0>¯¯
2 ¯ ¯
5 5
¯ ¯2
¯ 2 ¯ 1 ¯ ¯
= ¯ √ < ψ2,1,0 ψ1,0,0> + √ < ψ2,1,0 ψ2,1,0>¯¯
¯ ¯ ¯
5 5
¯ ¯2
¯ 1 ¡ ¢¯ 1
= ¯¯0 + √ 1 ¯¯ = .
5 5
¡ ¢ ¡ ¢
Notice the sum of the probabilities is 1, P E = −13.6 eV + P E = −3.4 eV = 4/5 + 1/5 = 1,
for example. Notice also, we use the normalized state vector, and the bra of the eigenstate serves
only to identify the eigenstate is being used for the calculation.
Lastly, there is but one possibility for z–component of angular momentum, corresponding to
m = 0 in both eigenstates, so we can conclude
¡ ¢
P Lz = 0 = 1,

355
without further calculation. Just to illustrate a calculation for which two eigenstates have the
same eigenvalue,
¯ ¯ ¯2 ¯ ¯ ¯2
¡ ¢ ¯ ¯ 2 1 ¯ ¯ ¯ 2 1 ¯
P Lz = 0 = ¯¯< ψ1,0,0 ¯¯ √ ψ1,0,0 + √ ψ2,1,0>¯¯ + ¯¯< ψ2,1,0 ¯¯ √ ψ1,0,0 + √ ψ2,1,0>¯¯
5 5 5 5
¯ ¯2 ¯ ¯2
¯ 2 ¯ ¯ ¯ 1 ¯ ¯
= ¯¯ √ < ψ1,0,0 ¯ψ1,0,0>¯¯ + ¯¯ √ < ψ2,1,0 ¯ψ2,1,0>¯¯
5 5
¯ ¯ ¯ ¯
¯ 2 ¡ ¢¯2 ¯ 1 ¡ ¢¯2
= ¯¯ √ 1 ¯¯ + ¯¯ √ 1 ¯¯
5 5
4 1
= + = 1.
5 5

There are two additional teaching points in exercise 10–16. If we have a more general linear
combination of eigenstates, say
X
Ψ= ci ψi = c1 ψ1 + c2 ψ2 + c3 ψ3 + · · ·
i

where the sum may terminate at some value n or be an infinite sum as indicated above. The ci
are expansion coefficients or more simply, the ci are individual normalization constants for
individual eigenstates. Generalizing from a two eigenstate system to a many eigenstate system,
the probability of measuring a property associated with one specific eigenstate, say eigenstate ψj ,
is ¯ ¯ ¯2 ¯ ¯ ¯2 ¯ ¯ ¯2 ¯ ¯2
P = ¯ < ψj ¯Ψ> ¯ = ¯ < ψj ¯c1 ψ1 + c2 ψ2 + c3 ψ3 + · · ·> ¯ = ¯cj < ψj ¯ψj > ¯ = ¯cj ¯ ,
¯
where the orthonormality condition < i|j> = δij tells us < ψj ¯ψj > = 1, and cross terms with
unlike indices are zero. Knowing this, the calculation for any property associated with ψ1,0,0 for
instance is ¯ ¯
¡ ¢ ¯ 2 ¯2 4
P ψ1,0,0 = ¯ ¯ √ ¯ =
5¯ 5
and the remainder of the symbology in the calculation is unnecessary.
¡ ¢
The second teaching point concerns the calculation of P Lz = 0 . Why do we use
¯ ¯ ¯2 ¯ ¯ ¯2
¡ ¢ ¯ ¯ 2 1 ¯ ¯ ¯ 2 1 ¯
P Lz = 0 = ¯< ψ1,0,0 ¯ √ ψ1,0,0 + √ ψ2,1,0>¯ + ¯< ψ2,1,0 ¯ √ ψ1,0,0 + √ ψ2,1,0>¯¯ ,
¯ ¯ ¯ ¯ ¯
5 5 5 5

and not ¯ ¯ ¯2
¯ ¯ ¯
¯< ψ1,0,0 + ψ2,1,0 ¯ √2 ψ1,0,0 + √1 ψ2,1,0>¯ ?
¯ ¯ 5 5 ¯

The answer, referring to equations (1–2) and (1–3), is a measurement will place a linear combination
into one specific eigenstate. We have a final state which is distinctly one of two eigenstates, and we
¯ ¯2 ¯ ¯2 ¯ ¯2
can ascertain from the measurement which one. That tells us ¯ψ ¯ = ¯ψa ¯ + ¯ψb ¯ . If we could not
uniquely distinguish a final state, a situation we will encounter in the circumstance of degeneracy,
¯ ¯2 ¯ ¯
¯ψ ¯ = ¯ψa + ψb ¯2 . One reason a complete set of commuting observables is important is to provide
a capability to uniquely distinguish final states, thus avoiding the indeterminacy associated with

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¯ ¯2 ¯ ¯
¯ψ ¯ = ¯ψa + ψb ¯2 , where we do not know what portion of the probability originates with which
eigenstate.

Expectation Value, Uncertainty and Time Dependence

Example 10–17: What are the expectation values of energy, orbital angular momentum, and
the z–component of angular momentum?
X 4¡ ¢ 1¡ ¢
< E> = P (Ei )Ei = − 13.6 eV + − 3.4 eV = −10.88 eV − 0.68 eV = −11.56 eV.
i
5 5
√
√ X 4 ¡ ¢ 1 ¡√ ¢ 2h̄
< L2> = P (αi )αi = 0 + 2h̄ = .
5 5 5
i
The expectation value of the z–component of angular momentum is 0, since that is the only
possibility.

Example 10–18: What are the uncertainties of energy, orbital angular momentum, and the
z–component of angular momentum?
sX
¡ ¢2
∆E = P (Ei ) Ei − < E>
i
· ¸
4¡ ¢2 1 ¡ ¢2 1/2
= − 13.6 eV − −11.56 eV + − 3.4 eV − −11.56 eV
5 5
· ¸ · ¸
4¡ ¢2 1 ¡ ¢2 1/2 4¡ ¢ 1¡ ¢ 1/2
= − 2.04 + 8.16 eV = 4.16 + 66.59 eV
5 5 5 5
1/2 1/2
= [3.33 + 13.32] eV = [16.65] eV
= 4.08 eV.
 Ã   Ã Ã √ !2 1/2
√ !2 Ã √ !2 1/2 √ !2
√ 4 2h̄ 1 √ 2h̄  4 2 1 4 2 
∆ L2 =  0− + 2h̄ − = − + h̄
5 5 5 5 5 5 5 5
· µ ¶ µ ¶¸1/2 · ¸1/2 · ¸1/2
4 2 1 16 · 2 8 32 40
= 2
+ 2
h̄ = 3 + 3 h̄ = 3 h̄
5 5 5 5 5 5 5
√
2 2
= h̄.
5
The uncertainty in the z–component of angular momentum is 0, since there is only one possibility.

Example 10–19: What is the time dependent state vector?

¯ X
¯Ψ(t)> = |j>< j|ψ(0)> e−iEj t/h̄
µ ¶ µ ¶ µ ¶ µ ¶
1 ¡ ¢ 1 2 −iE1 t/h̄ 0 ¡ ¢ 1 2
= 1, 0 √ e + 0, 1 √ e−iE2 t/h̄
0 5 1 1 5 1
µ ¶ µ ¶
1 1 ¡ ¢ −iE1 t/h̄ 0 1 ¡ ¢
= √ 2 e + √ 1 e−iE2 t/h̄
0 5 1 5
µ ¶ µ ¶
2 1 1 0
=√ e−iE1 t/h̄ + √ e−iE2 t/h̄ ,
5 0 5 1

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and using eigenenergies in terms of fundamental constants, i.e.,

h̄2
En = − ,
2µa20 n2

this becomes µ ¶ µ ¶
¯
¯Ψ(t)> = √2 1
e ith̄/2µa20 1
+√
0 2
eith̄/8µa0 .
5 0 5 1

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