1 The Hydrogen Atom

1. Important Relations

(a) Integrals
(b) Probability Density
(c) Orthonormalization Relations
(d) Electric and Magnetic Moments

2. Solved Problems
Problem 1.1
Using the radial wave functions
2
R10 = p 3 e−r/aB
aB
 
1 r
R20 = p 3 1 − e−r/2aB
2aB 2aB
1 r −r/2aB
R21 = p 3 e
24aB aB

evaluate the following integrals and explain what the results imply.
R∞
(a) 0
R10 R10 r2 dr
R∞
(b) 0
R10 R20 r2 dr
R∞
(c) 0
R10 R21 r2 dr
R∞
(d) 0
R20 R21 r2 dr

Solution

(a) Using the expression for R10 , the first integral can be written as
Z ∞ Z ∞
4
2
R10 R10 r dr = 3 r2 e−2r/aB dr (1.1)
0 a B 0

Applying the general relation

Z ∞
n!
rn e−br dr = (1.2)
0 bn+1

1
 one can see that
Z ∞
4 2!
R10 R10 r2 dr = 3
× 2 3 = 1. (1.3)
0 aB ( a B )
This result can be interpreted in different ways depending on what we
want to emphasize. The radial wave function R10 is properly normalized,
This interpretation emphasizes the fact that the function is convenient for
statistical interpretation. The probability of finding the electron around
the proton at any radial distance is one, which emphasizes the fact that
the electron is bound.
(b) Using the expressions for R10 and R20 , the second integral can be written
as
Z ∞ Z ∞ Z ∞ 
2 2 1 2 −3r/2aB 1 3 −3r/2aB
R10 R20 r dr = √ 3 r e dr − r e dr
0 2 aB 0 2aB 0
 
2 1 2! 1 3!
= √ 3 −
2 aB ( 2a3B )3 2aB ( 2a3B )4
= 0 (1.4)

R10 and R20 orthogonal or non-overlapping functions. Note that the two
functions have different n values but the same l value.
(c) Using the expressions for R10 and R21 , the third integral can be written as
Z ∞ Z ∞
2 1
2
R10 R21 r dr = √ 4
r3 e−3r/2aB dr
0 a
24 B 0
2 1 3!
= √
24 a4B ( 2a3B )4
32
= √ (1.5)
27 6
Note that the two functions have different n and l values. However, they
are not orthogonal. They are overlapping functions.
(d) Using the expressions for R20 and R21 , the third integral can be written as
Z ∞ Z ∞ Z ∞ 
2 1 1 3 −r/aB 1 4 −r/aB
R20 R21 r dr = √ r e dr − r e dr
0 48 a4B 0 2aB 0
 
1 1 3! 1 4!
= √ −
48 a4B ( a1B )4 2aB ( a1B )5
3!

= √ 1−2
4 3
3
= −√ (1.6)
3

2
 Note that the two functions have the same n value but different l values.
However, they are not orthogonal. In general, two radial wave functions
are orthogonal if they have different n values but the same l value.

Problem 1.2
For a hydrogen atom in the ground state, calculate the following quantities and
discuss the results:

(a) the most probable radial distance of the electron r10 ,

(b) the expectation value of r,
(c) the probability the electron being in the region r < r10 .

Solution

(a) The most probable radial distance is the radial distance at which the
radial probability density is maximum. For a hydrogen atom in one of the
stationary states Ψnlm (r, θ, φ) = Rnl (r)Ylm (θ, φ), the radial probability
density is given by
2
Pnl (r) = Rnl (r)r2 (2.1)

Differentiating with respect to r, one can see that

 
dPnl (r) dRnl (r)
= 2rRnl (r) Rnl (r) + r (2.2)
dr dr

The most probable radial distance is determined by solving

 
dRnl (r)
Rnl (r) + r =0 (2.3)
dr r=rnl

For a hydrogen atom in the ground state, the radial wave function is
R10 (r) = √2 3 e−r/aB . Hence replacing Rnl (r) by R10 (r), one can arrive at
aB

 
r10 2
1− p e−r10 /aB = 0 (2.4)
aB a3B

from which follows r10 = aB .

For a hydrogen atom in the ground state, the most probable value of r is
aB , which is equal to the radius of the first allowed circular orbit in Bohr
model. However, in contrast to Bohr’s picture, the electron may be found

3
 at values of r greater or smaller than aB . In modern quantum theory of
atomic structure, the electron in a hydrogen atom does not travel in a
well-defined orbit about the proton. Instead, it occupies a state called
orbital, which may be visualized as a cloud of negative electricity
surrounding the proton.
(b) For a hydrogen atom in the ground state, the expectation value of r is
Z ∞
hri10 = R10 (r)rR10 (r)r2 dr (2.5)
0
Z ∞
4
= 3 r3 e−2r/aB dr (2.6)
aB 0
Now employing the general relation
Z ∞
n!
rn e−br dr = n+1 (2.7)
0 b

4 3!
hri10 = 3
aB (2/aB )4
3
= aB . (2.8)
2
Note that the most probable radial distance is less than the expectation
value of r. This difference indicates that the radial probability distribution
is not symmetric about the most probable radial distance. One can also
assert that the probability of finding the electron between r = 0 and r = aB
is less than the probability of finding the electron r = aB and r = ∞.
(c) The probability of finding the electron between r = 0 and r = aB is
Z aB
P0,aB = R10 (r)R10 (r)r2 dr
0
Z aB
4
= 3 r2 e−2r/aB dr (2.9)
aB 0
In evaluating this integral, it more convenient to introduce the
dimensionless variable ρ = 2r/aB . In terms of this variable, Eq. (2.9) can
be rewritten as
1 2 2 −ρ
Z
P0,aB = ρ e dρ. (2.10)
2 0
Now let’s consider the general indefinite integral
Z k=n
n −ρ −ρ
X n!
ρ e dρ = −e ρn−k (2.11)
k=0
(n − k)!

4
 where ρ is a dimensionless variable and k = 0, 1, , . . . , n. For n = 2, this
internal leads to
Z k=2
2 −ρ −ρ
X 2!
ρ e dρ = −e ρ2−k
(2 − k)!
k=0 
−ρ 2
= −e ρ + 2ρ + 2 (2.12)

Employing this relation,

 2
1 −ρ 2
P0,aB = − e (ρ + 2ρ + 2)
2 0
 
1 −2
= − e (4 + 4 + 2) + 2
2
= 1 − 5e−2
≈ 0.323 (2.13)

The probability of finding the electron between r = 0 and the most

probable radial distance r10 = aB is less than 0.5. This result confirms that
the radial probability density is not symmetric about the most probable
distance. Moreover, one can also show that the radial probability density
is not symmetric about hri10 .

Problem 1.3
The state of a hydrogen atom at t = 0 is given by the state vector
√ √ √
3 i 5 2
|Ψ(0)i = √ |2, 1, −1i − √ |2, 1, 0i + √ |2, 1, 1i + √ |3, 1, 1i,
11 11 11 11
where |2, 1, −1i, |2, 1, −1i, |2, 1, −1i, and |2, 1, −1i are the common eigenvectors
of Ĥ, L̂2 , and L̂z .

(a) Write the expression for the state vector |Ψ(t)i at any later time.
(b) Is |Ψ(0)i normalized? Does is remain normalized at any later time?
(c) If a measurement of energy is made, what values could be found and with
what probabilities?
(d) Repeat question (c) for the magnitude of the orbital angular momentum
and its z component.

5
Solution

(a) The state vector |Ψ(0)i is described as the superposition of four stationary
states. Three of these states have the same energy E2 = −13.6 eV /4. The
fourth stationary state has energy E3 = −13.6 eV /9. Hence, the state
vector evolves in time according to
√
3 i
|Ψ(t)i = √ |2, 1, −1ie−iE2 t/h̄ − √ |2, 1, 0ie−iE2 t/h̄
11 11
√ √
5 2
+ √ |2, 1, 1ie−iE2 t/h̄ + √ |3, 1, 1ie−iE3 t/h̄
11 11
(b) The normalization of the state vector |Ψ(0)i is determined by calculating
the inner product the state vector and its Hermitian conjugate hΨ(0)|:
√ √ √ 
3 i 5 2
hΨ(0)|Ψ(0)i = √ h2, 1, −1| + √ h2, 1, 0| + √ h2, 1, 1| + √ h3, 1, 1|
11 11 11 11
√ √ √ 
3 i 5 2
× √ |2, 1, −1i − √ |2, 1, 0i + √ |2, 1, 1i + √ |3, 1, 1i
11 11 11 11
Note that the state vector |Ψ(0)i is the superposition four stationary
stationary that are orthonormal, which is mathematically described by

hn, l, m|n0 , l0 , m0 i = δnn0 δll0 δmm0

Employing this relation, one can see that

 √  √    
3 3 i −i
hΨ(0)||Ψ(0)i = √ √ + √ √
11 11 11 11
 √  √   √  √ 
5 5 2 2
+ √ √ + √ √ =1
11 11 11 11
This result indicates that the sate vector is normalized. Similarly, one can
also show that
hΨ(t)||Ψ(t)i = 1
From this result, one can learn that if a state vector is normalized at t = 0,
it remains normalized at any latter time t.
(c) If the energy of the hydrogen atom is measured, one would obtain either
E2 or E3 . Since there three states of the same energy, the probability of
getting E2 is
 √  √      √  √ 
3 3 i −i 3 3 9
PE=E2 = √ √ + √ √ + √ √ =
11 11 11 11 11 11 11

6
 The probability of getting E3 is
 √  √ 
2 2 2
PE=E3 = √ √ = .
11 11 11

(d) Employing the relations

L̂2 |n, l, mi = l(l + 1)h̄2 |n, l, mi

L̂z |n, l, mi = mh̄|n, l, mi

one can show that

L̂2 |Ψ(t)i = 2h̄2 |Ψ(t)i
√
3 i
L̂z |Ψ(t)i = −h̄ √ |2, 1, −1ie−iE2 t/h̄ − 0 √ |2, 1, 0ie−iE2 t/h̄
11 11
√ √
5 2
+h̄ √ |2, 1, 1ie−iE2 t/h̄ + h̄ √ |3, 1, 1ie−iE3 t/h̄
11 11
From these results, one can see the hydrogen atom is in state in which the
magnitude of the orbital angular momentum vector is well defined. The
√
measurement of this quantity definitely yields 2h̄. The z-component,
however, is not well defined. The possible outcomes of the measurement
of the z-component are Lz = 0, h̄, and −h̄. The probabilities of getting
each these results are
1
PLz =0 =
11
7
PLz =h̄ =
11
3
PLz =−h̄ =
11

Problem 1.4
Consider a hydrogen atom whose wave function is given at t = 0 by
 3/2  
A 1 −r/aB 1 z (x + iy)
Φ(~r, 0) = √ e +√ + √ R21 (r),
π aB 8π r 2r
where A is a real positive constant, and aB is the Bohr radius.

(a) Write Ψ(~r, 0) in terms of the stationary wave functions

Ψnlm (r, θ, φ) = Rnl (r)Ylm (θ, φ).

7
(b) Find A so the Ψ(~r, 0) is normalized.
(c) Write the expression for Ψ(r, θ, φ).

Solution

(a) To express Φ(~r, 0) in terms of stationary states in spherical coordinates,

one is expected to note the following relations:

x + iy = r sin θeiφ (4.1)

r
−1 3
Y1 (θ, φ) = − sin θeiφ (4.2)
8π
z = r cos θ (4.3)
r
3
Y20 (θ, φ) = cos θ (4.4)
4π
Based on these relations, we obtain
r
8π
x + iy = −r (4.5)
3
r
4π
Z = r cos θ (4.6)
3
Moreover on one is expected to note that in any stationary state the radial
wave function involves a polynomial function in r and an exponential
function e−r/naB , where n is the principal quantum number. In this case
the exponential function in the first term is e−r/aB . Hence on is expected
to use the ground state wave function
1
Ψ100 (r, θ, φ) = p e−r/aB (4.7)
πa3B
Using these relations, Φ(~r, 0) can be written as
1 1
Φ(~r, 0) = Ψ(r, θ, φ, 0) = AΨ100 (r, θ, φ) + √ Ψ210 (r, θ, φ) − √ Ψ211 (r, θ, φ)
6 12
(4.8)
(b) The wave function at t = 0 is normalized if
Z ∞ Z π Z 2π
Ψ∗ (r, θ, φ, 0)Ψ(r, θ, φ, 0)r2 sin θdrdθdφ = 1 (4.9)
0 0 0

The stationary states Ψ100 (r, θ, φ), Ψ100 (r, θ, φ) and Ψ100 (r, θ, φ) are
orthonormal. Hence Eq. (4.9) leads to
1 1
A2 + + = 1, (4.10)
6 12

8
 q
3
from follows A = 4
. The normalized wave function then takes the form
r
3 1 1
Φ(~r, 0) = Ψ(r, θ, φ, 0) = Ψ100 (r, θ, φ) + √ Ψ210 (r, θ, φ) − √ Ψ211 (r, θ, φ)
4 6 12
(4.11)
(c) The wave function evolves in time according to
r
3
Ψ(r, θ, φ, t) = Ψ100 (r, θ, φ)e−iE1 t/h̄
4
1 1
+ √ Ψ210 (r, θ, φ)e−iE2 t/h̄ − √ Ψ211 (r, θ, φ)e−iE2 t/h̄ (4.12)
6 12

Problem 1.5
For a hydrogen atom in any stationary state, show that

(a) hxinlm = hyinlm = hzinlm = 0,

(b) hxyinlm = hxzinlm = hyzinlm = 0,
(c) hx2 inlm = hy 2 inlm .

Solution

(a) In position space, the starting equations in calculating the expectation

values of x, y, and z in any stationary state are
Z
hxinlm = Ψ∗nlm (~r)x̂Ψnlm (~r)dv (5.1)
v

In spherical coordinates,

x̂ → x = r sin θ cos φ (5.2)

Z Z ∞ Z π Z 2π
→ (5.3)
v 0 0 0

dv → r2 sin θdrdθdφ (5.4)

Ψnlm (~r) → Ψnlm (r, θ, φ) (5.5)

Employing these relations, the Eq. (5.1) take the forms

Z ∞ Z π Z 2π
hxinlm = Ψ∗nlm (r, θ, φ)r sin θ cos φΨnlm (r, θ, φ)r2 sin θdrdθdφ
0 0 0
(5.6)

9
In spherical coordinates, a stationary state function can be written as a
product of the radial and angular functions that are normalized
separately:
Ψnlm (r, θ, φ) = Rnl (r)Ylm (θ, φ) (5.7)

In calculating expectation values, it is more convenient to write Eq. (5.7)

as a product of three normalized functions:

Ψnlm (r, θ, φ) = Rnl (r)Flm (θ)Gm (φ) (5.8)

where Flm (θ) is a normalized real function of θ whose explicit form

depends on the quantum numbers l and m ;
Z π
2
Flm (θ) sin θdθ = 1, (5.9)
0

e√imφ
Gm (φ) = 2π
is a normalized complex function of φ which depends on the
quantum number m only:
Z 2π
G∗m (φ)Gm (φ) = 1. (5.10)
0

Now introducing Eq. (5.8) and its complex conjugate into Eq. (5.6), the
expectation value of x can be written as a product three expectation
values that can be calculated separately:

hxinlm = hrinl hsin θilm hcos φim (5.11)

where
Z ∞
hrinl = r3 Rnl
2
(r)dr 6= 0 (5.12)
0
Z π
hsin θilm = sin2 θFlm
2
(θ)dθ 6= 0 (5.13)
0
Z 2π Z 2π
1
hcos φim = G∗m (φ) cos φGm (φ)dφ = cos φdφ = 0 (5.14)
0 2π 0

In view of these result along with Eq. (5.11), the expectation value of x in
any stationary state is zero:
hxinlm = 0 (5.15)

From this result one can learn that the probability density symmetric
about x = 0 in any stationary state.

10
Note the radial distance r is non-negative. Since 0 ≤ θ ≤ π, sin θ is also
non-negative. In general, the expectation value of a non-negative
quantity in any stationary state or superposition of stationary states is
different from zero. The expectation value a quantity that may take
positive as well as negative values may or may not be zero.
In spherical coordinates, ŷ → y = r sin θ cos φ. Since
Ψnlm (r, θ, φ) = Rnl (r)Flm (θ)Fm (φ) , the expectation value of y in any
stationary state can be written as

hyinlm = hrinl hsin θilm hsin φim (5.16)

where Z 2π
1
hsin φim = sin φdφ = 0 (5.17)
2π 0

In view of this result, Eq. (5.16) reduces to

hyinlm = 0 (5.18)

In spherical coordinates z = r cos θ. Hence its expectation value in any

stationary state can be written as

hzinlm = hrinl hcos θilm (5.19)

where Z π
2
hcos θilm = cos θ sin θFlm (θ)dθ (5.20)
0

Replacing cos θ sin θ by 21 sin(2θ), Eq. (5.20) can be rewritten as

1 π
Z
2
hcos θilm = sin(2θ)Flm (θ)dθ (5.21)
2 0

In any stationary state, the expectation value of r is different from zero.

Hence the expectation value of z is zero only if the expectation value of
2
cos θ or the integral over θ is zero. For the state in which l = 0, F00 = 1/2. In
this state one can easily see that integral over θ is zero. For states with
2
l ≥ 1, Flm (θ) can be written as a function cos2 θ or sin2 θ. Hence Flm
2
(θ) is an
2 2
even function of θ. That is, Flm (θ) = Flm (−θ).
In order to evaluate this integral, we first introduce a new variable
2 2
α = θ − π/2. In terms of this variable, sin(2θ) → − sin(2α); Flm (θ) → Flm (α);

11
 dθ → dα; the lower and the upper limits of integration become −π/2 and
π/2, respectively. Hence Eq. (5.21) takes the form
Z π/2
2
hcos θilm = − sin(2α)Flm (α)dα (5.22)
−π/2

from which follows

Z 0 Z π/2
2 2
hcos θilm = − sin(2α)Flm (α)dα − sin(2α)Flm (α)dα (5.23)
−π/2 0

Interchanging the upper and lower limits in the first integral

Z −π/2 Z π/2
2 2
hcos θilm = sin(2α)Flm (α)dα − sin(2α)Flm (α)dα (5.24)
0 0

Replacing α by −α in the first integral and employing the fact that

2 2
Flm (−α) = Flm (α)
Z π/2 Z π/2
2 2
hcos θilm = sin(2α)Flm (α)dα − sin(2α)Flm (α)dα = 0 (5.25)
0 0

In view of this result Eq. (5.19) reduces to

hzinlm = 0 (5.26)

(b) In spherical coordinates, x̂ŷ → xy = r2 sin2 θ cos φ sin φ = 21 r2 sin2 θ sin(2φ).

Employing the fact that the stationary state wave function is separable,
the expectation value of xy in any stationary state can be written as
1
hxyinlm = hr2 inl hsin2 θilm hsin(2φ)im (5.27)
2
where Z ∞
2
hr inl = r4 Rnl
2
(r)dr 6= 0 (5.28)
0
Z π
2
hsin θilm = sin3 θFlm
2
(θ)dθ 6= 0 (5.29)
0
Z 2π
1
hsin(2φ)im = sin(2φ)dφ = 0. (5.30)
2π 0

In view of Eq. (5.30) along with Eq. (5.27), one can see that the expectation
value of xy in any stationary state is zero.
Similarly, one can also show that hxzi = hyzi = 0.

12
 (c) In spherics coordinates, the expectation values of x2 and y 2 in any
stationary state can be written as

hx2 inlm = hr2 inl hsin2 θilm hcos2 φim (5.31)

hy 2 inlm = hr2 inl hsin2 θilm hsin2 φim (5.32)

where
Z 2π
2 1
hcos φim = cos2 φdφ
2π 0
 Z 2π Z 2π 
1
= dφ + cos(2φ)dφ
4π 0 0
1
= (5.33)
2

Z 2π
2 1
hsin φim = sin2 φdφ
2π 0
 Z 2π Z 2π 
1
= dφ − cos(2φ)dφ
4π 0 0
1
= (5.34)
2
One can then see that in any stationary state, the expectation values x2
and y 2 are equal and non-zero.

Problem 1.6
The state of an electron in the hydrogen atom is described by

|Ψ(t)i = c1 |1, 0, 0ie−iE1 t/h̄ + c2 |2, 1, 1ie−iE2 t/h̄

where |c1 |2 + |c2 |2 = 1.

(a) Show the given state vector can also be written as

|Ψ(t)i = c1 |1, 0, 0i + c2 |2, 1, 1ie−iΩt

or
|Ψ(t)i = c1 |1, 0, 0ieiΩt + c2 |2, 1, 1i

where Ω = (E2 − E1 )/h̄

13
(b) Write the expression for the expatiation value of an arbitrary Hermitian
operator  and interpret the four terms that appear in this expression.
~ = −e~r. Take
(c) Find the expectation value of the electric dipole moment D
c1 = c2 = √1 .
2

(d) What does Ω represents?

Solution

(a) The given state vector can be written as

 
−iE1 t/h̄ −i(E2 −E1 )t/h̄
|Ψ(t)i = e c1 |1, 0, 0i + c2 |2, 1, 1ie (6.1)

or  
−iE2 t/h̄ i(E2 −E1 )t/h̄
|Ψ(t)i = e c1 |1, 0, 0ie + c2 |2, 1, 1i (6.2)

Both expressions are mathematically the same. However, the first

expression is written with e−iE1 t/h̄ as global phase factor while the second
expression is written with e−iE2 t/h̄ as a global factor. In both expressions,
the global phase factors have no physical relevance. They cancel out
whenever one calculates a measurable quantity. Hence dropping the
global phase factor in each expression and then replacing (E2 − E1 )/h̄ by
Ω we get
|Ψ(t)i = c1 |1, 0, 0i + c2 |2, 1, 1ie−iΩt (6.3)
or
|Ψ(t)i = c1 |1, 0, 0ieiΩt + c2 |2, 1, 1i (6.4)

(b) Using sate vector |Ψ(t)i described by Eq. (6.3) and its Hermitian
conjugate, the expectation of A can be written as

hAi = hΨ(t)|Â|Ψ(t)i
   
∗ ∗ iΩt −iΩt
= c1 h1, 0, 0| + c2 h2, 1, 1|e  c1 |1, 0, 0i + c2 |2, 1, 1ie

= |c1 |2 h1, 0, 0|Â|1, 0, 0i + |c2 |2 h2, 1, 1|Â|2, 1, 1i

+c∗1 c2 h1, 0, 0|Â|2, 1, 1ie−iΩt + c∗2 c1 h2, 1, 1|Â|1, 0, 0ieiΩt (6.5)

• The first term represents the expectation value of A in the ground

state. The real coefficient |c1 |2 in this term represents the probability
of finding the electron in the ground state.

14
 • The second term represents the expectation value of A in the first
excited state. The real coefficient |c2 |2 represents the probability of
finding the electron in the first excited state.
• In the second and third terms, the operator  is sandwiched between
the ground and the first excited state vectors in different orders. These
sandwiches are called matrix elements of operator Â.
• The two matrix elements are complex conjugates of each other:
h2, 1, 1|Â|1, 0, 0i = h1, 0, 0|Â|2, 1, 1i∗
• The expectation value of A evolves with time only if its matrix
elements are non-zero.
• If the matrix elements of A are non-zero, the angular frequency Ω (also
called the Bohr frequency) indicates the frequency of the photon that
can be emitted or absorbed by the atom.
(c) Since the electric diploe is a vector, its expectation value can be written as
a vector sum of the expectation values of its components;

~ = Dx î + Dy ĵ + Dz k̂ = −e(hxiî + hyiĵ + hzik̂)

hDi (6.6)

Now using Eq. (6.5), one can see that

hxi = |c1 |2 h1, 0, 0|x̂|1, 0, 0i + |c2 |2 h2, 1, 1|x̂|2, 1, 1i

+c∗1 c2 h1, 0, 0|x̂|2, 1, 1ie−iΩt + c∗2 c1 h2, 1, 1|x̂|1, 0, 0ieiΩt (6.7)
hyi = |c1 |2 h1, 0, 0|ŷ|1, 0, 0i + |c2 |2 h2, 1, 1|ŷ|2, 1, 1i
+c∗1 c2 h1, 0, 0|ŷ|2, 1, 1ie−iΩt + c∗2 c1 h2, 1, 1|ŷ|1, 0, 0ieiΩt (6.8)
hzi = |c1 |2 h1, 0, 0|ẑ|1, 0, 0i + |c2 |2 h2, 1, 1|ẑ|2, 1, 1i
+c∗1 c2 h1, 0, 0|ẑ|2, 1, 1ie−iΩt + c∗2 c1 h2, 1, 1|ẑ|1, 0, 0ieiΩt (6.9)

In Problem 1.5, we have shown that in any stationary state

hxinlm = hyinlm = hzinlm = 0. Moreover, the two matrix elements in each
equation are complex conjugates of each other. Employing these facts and

15
 √
taking c1 = c2 = 1/ 2, Eqs. (6.7-6.9) can be written as
 
1 ∗
hxi = h1, 0, 0|x̂|2, 1, 1i + h1, 0, 0|x̂|2, 1, 1i cos Ωt
2
 
i ∗
− h1, 0, 0|x̂|2, 1, 1i − h1, 0, 0|x̂|2, 1, 1i sin Ωt (6.10)
2
 
1 ∗
hyi = h1, 0, 0|ŷ|2, 1, 1i + h1, 0, 0|ŷ|2, 1, 1i cos Ωt
2
 
i ∗
− h1, 0, 0|ŷ|2, 1, 1i − h1, 0, 0|ŷ|2, 1, 1i sin Ωt (6.11)
2
 
1 ∗
hzi = h1, 0, 0|ẑ|2, 1, 1i + h1, 0, 0|ẑ|2, 1, 1i cos Ωt
2
 
i ∗
− h1, 0, 0|ẑ|2, 1, 1i − h1, 0, 0|ẑ|2, 1, 1i sin Ωt (6.12)
2
Matrix elements of x
Z 2π Z π Z ∞
h1, 0, 0|x̂|2, 1, 1i = Ψ∗100 xΨ211 r2 sin θdrdθdφ (6.13)
0 0 0

In spherical coordinates,

x = r sin θ cos φ (6.14)

1
Ψ100 = √ 3 e−r/a2 (6.15)
πaB
1 r −r/2aB
Ψ211 = − p 3 e sin θeiφ (6.16)
8 πaB B a

Introducing Eqs. (6.14-6.16) into Eq. (6.13), we have

Z 2π Z π Z ∞
1
h1, 0, 0|x̂|2, 1, 1i = − 4
iφ
cos φe dφ 2
sin θdθ r4 e−3r/2aB dr
8πaB 0 0 0
(6.17)
Evaluation the integrals over φ, θ, and r, one obtains the following results:

Z 2π Z 2π Z 2π
iφ 2
cos φe dφ = cos φdφ + i cos φ sin φdφ
0 0 0
1 2π 1 2π i 2π
Z Z Z
= dφ + cos 2φdφ + sin 2φdφ
2 0 2 0 2 0
= π (6.18)

Z π Z π Z π
2 1 1
sin θ = dθ − cos 2θdθ = π/2 (6.19)
0 2 0 2 0

16
 ∞
4!25 a5B
Z
4!
r4 e−3r/2aB dr = = (6.20)
0 ( 2a3B )5 35

Introducing these results into Eq. (6.17), one can see that
16π
h1, 0, 0|x̂|2, 1, 1i = − aB (6.21)
91
Note that this matrix element is real. Hence
16π
h1, 0, 0|x̂|2, 1, 1i = h1, 0, 0|x̂|2, 1, 1i∗ = − aB (6.22)
91
In view of this result along with Eq. (6.10) we arrive at
16π
hxi = − aB cos Ωt (6.23)
91
16πe
hDx i = aB cos Ωt (6.24)
91

Similarly, one can also show that

16π
h1, 0, 0|ŷ|2, 1, 1i = −i aB
91
h1, 0, 0|ẑ|2, 1, 1i = 0

from which follows

16πe
hDy i = aB sin Ωt
91
hDz i = 0

Finally, the expectation value of the electric dipole vector can be written as
 
~ = 16πe
hDi aB ~i cos Ωt + ~j sin Ωt
91

The expecting value of the electric dipole rotates in the xy plane about the
z axis in the counterclockwise direction with angular speed omega. the
angular frequency of the emitted radiation is

17