The hydrogen atom consists of a proton of mass m

p
=1.710
-27
kg and charge q
e
=1.610
-
19
C and an electron of mass m
e
=9.110
-31
kg and charge -q
e
. The dominant part of the
interaction between the two particles is the electrostatic interaction. The
electrostatic potential energy is

in SI units.
If we confine ourselves to studying the relative motion of the two particles, and if we
neglect any external forces, and if we treat the particles as spinless particles, then
the Hamiltonian of the system is
.
The reduced mass of the system is nearly the same as the electron mass m
e
, and the
center of mass of the system is nearly in the same place as the proton. We therefore
often call the relative particle "the electron" and the center of mass "the proton".
The eigenvalues and eigenfunctions of H(r,p)
.
H is the Hamiltonian of a fictitious particle moving in a central potential. We already
know that the eigenfunctions of H are of the form
,
where u
kl
(r) satisfies the radial equation

with the condition u
kl
(0)=0.
We define the effective potential .

In terms of the effective potential the radial equation becomes
.
As r approaches infinity, V
eff
(r) goes to zero. For every E
kl
>0 there therefore exists a
solution u
kl
(r) with an oscillatory behavior at infinity. These solutions represent
unbound states.
For E
kl
<0 u
kl
(r) will be proportional to as r approaches infinity. The
real positive exponential solution is physically unacceptable. As r goes to zero, u
kl
(r)
becomes proportional to r
l+1
. Only for certain discrete values of E
kl
is it possible to
properly match these two asymptotic solutions.
In order to simplify the radial equation, we introduce the dimensionless
quantity , where . The radial equation then
becomes
.
We want to solve this equation for E
kl
<0 to find the energies of the bound states of
the hydrogen atom.
Defining

we have
.
We therefore try a solution of the form
.
_
kl
satisfies the equation
.
We have
.
Therefore
.
We may write this as .
The coefficients a
q
for each power q of must vanish for this to hold for all . For
the power q+l-1 we therefore must have
. .
We have found a recurrence relation for the coefficients c
q
. Fixing c
0
allows us to
calculate all c
q
.
We have
.
As .
This implies that as _
kl
() becomes proportional to , since
.
The asymptotic behavior of u
kl
() is then dominated by which is physically
unacceptable.
In order to keep the wavefunction finite at infinity the power series defining
must terminate. For some integer q=k we need c
k
=0. We then have c
k
(q>k)=0. For
c
k
=0 we need .
Since we require c
0
to be non zero, the possible values for k are k=1, 2, 3, . For a
given l the possible values of E
kl
then are .
_
kl
() is a polynomial whose lowest order term is
l
+1and whose highest order term is

k+l
.
In terms of c
0
the various coefficients c
q
are calculated using the recurrence relations
.
.
.
The associate Laguerre polynomials are defined as
.
We therefore have
.
_
kl
() is proportional to a polynomial of order k-1 and therefore has k-1 radial nodes.
For u
kl
() we have
.
. Normalization requires .
.
We therefore have
.
.
Energy levels
For each l there exists an infinite number of possible energies, corresponding to
values of k=1, 2, 3, . Each of them is at least 2l+1 fold degenerate. This is the
essential degeneracy, since E
kl
does not depend on m. Accidental degeneracies also
exist. For the hydrogen atom we find that E
kl
is only a function of k+l, and we define
k+l=n for the hydrogen atom.
The possible eigenenergies therefore are . Here n is called
the principal quantum number, n fixes the energy of the eigenstate. Given n, l can
take on n possible values . n characterizes an electron shell,
which contains n subshells characterized by l. Each subshell contains 2l+1 distinct
states.
The total degeneracy of the energy level E
n
is
for a hydrogen atom made from spinless particles.
Links:
The wavefunctions of the hydrogen atom
Probability densities (1)
Probability Densities (2)
The hydrogen atom

Definitions and notations
The ground state energy of the hydrogen atom is -E
I
.

where
.
o is the fine structure constant.
.
We also have
.
R
H
is the Rydberg constant.
.
We denote the energy eigenstates of the hydrogen atom by { |n,l,m> }, where
n=k+l. The corresponding eigenfunctions are usually written as
.
, where k=n-l, and u
kl
(r) is given above. The number of radial nodes of
R
nl
(r) is n-l-1.

Spectroscopic notation
Letters of the alphabet are associated with various values of l.

l=0 s
l=1 p
l=2 d
l=3 f
l=4 g
Continue in alphabetic order.
The subshells are denoted by:
n l subshell
n=1 l=0 1s
n=2 l=0 2s
n=2 l=1 2p
etc.
The principal shells are denoted by:
n
principal
shell
n=1 K-shell
n=2 L-shell
n=3 M-shell
Continue in alphabetic order.
Problem:
In the interstellar medium electrons may recombine with protons to form hydrogen
atoms with high principal quantum numbers. A transition between successive values
of n gives rise to a recombination line.
(a) A radio recombination line occurs at 5.42597810
10
Hz for a n=50 to n=49
transition. Calculate the Rydberg constant for H.
(b) Compute the frequency of the H recombination line corresponding to the
transition n=100 to n=99.
(c) Assume the mean velocity in part (b) is 10
6
m/s. At what frequency or frequencies
would the recombination line be observable?
(d) Consider that radio recombination lines may be observed at either of two
facilities, the 11 meter telescope at Kitt Peak near Tuscon, Arizona, and the 1.2
meter radio telescope at Columbia University in New York. Relative larger blocks of
time are available on the smaller telescope, but its intrinsic noise is moderately
high. Where would you choose to map recombination radiation emanating from an
external galaxy. Discuss both technical and non technical aspects of your choice.
Solution:
(a)
.
(b) .
(c) The line is Doppler shifted.
if .
Here v is the relative velocity of source and observer; v is positive if the source and
the observer approach each other, and v is negative if the source and the receiver
recede from each other.

-6.65710
9
s
-1
svs6.70210
9
s
-1
.
(d) Here are some factors worth considering.
The amount of radiation gathered by a telescope is proportional to the square of its
diameter D.
The smallest angle that can be resolved is approximately .
(For each photon we have . .)
If you assume that the radiation has a frequency of , then
. For the small telescope we therefore have while for the large
telescope we have .
It takes times as long to gather the same amount of radiation with the
small telescope as with the large telescope.



..
.

Problem 1:
Assume that the potential energy of the deuteron is given by
V(r) = -V
0
, r < r
0
; V(r) = 0, r r
0
.
(a) Show that the ground state of the deuteron possesses zero orbital angular
momentum (l = 0). Since this is true for any central potential, you may not need the
detailed nature of the square well potential.
(b) Assume that l = 0 and estimate the value of V
0
under the additional condition that
the value of the binding energy is much smaller than V
0
.
Solution:
Concepts:
Three-dimensional square potentials
Reasoning:
We have to investigate the properties of the ground state in a three dimensional
square potential.
Details of the calculation:
(a) The Hamiltonian of the relative motion of the two particles is
.
.
Let
l
be the lowest energy eigenfunction of H with orbital angular momentum
quantum number l.
.
Let
l+1
be the lowest energy eigenfunction of H with orbital angular momentum
quantum number l + 1.
.
.

since
l
is assumed to be the lowest energy eigenfunction of the Hamiltonian
H
0
+ l(l+1)
2
/(2r
2
).
[The operator H
0
+ l(l+1)
2
/(2r
2
) = p
r
2
/(2) +V'(r) does not operate on the angular
coordinates. We can write its eigenfunctions as [u(r)/r]f(,), where f(,) is
arbitrary. The eigenvalues are determined by
(-
2
/(2))(d
2
/dr
2
)u(r) + V'(r)u(r) = Eu(r). By assumption, the lowest energy
eigenfunction u(r) is u
l
(r).]
Therefore E
l
min
E
l+1
min
and the ground state possesses zero orbital angular
momentum.
(b) The relative motion of the two particles is described in the same way as the
motion of a fictitious particle of reduced mass m in a central potential. Therefore
we have
.
.
The problem is reduced to a one dimensional "square well problem" with E < 0.

Let
.
Let r < r
0
define region 1 and r > r
0
define region 2. The coordinate r is never
negative. Therefore
.
.
The boundary conditions are
.
.
,
in regions where cotkr
0
< 0.
If we plot f(k) = |sinkr
0
| and g(k) = k/k
0
we find solutions at the intersections of the
two curves in regions where cotkr
0
< 0 , i.e.
.
For only one solution to exist we need the following condition for the slope 1/k
0
.
.

If |E|<<|V
0
| then k/k
0
~ 1. Then |sinkr
0
| ~ |sink
0
r
0
| = 1, k
0
r
0
~ /2.
.
Problem 2:
Find the condition that must be satisfied by the spherically symmetric square well
potential
V(r) = -|V
0
| for r < a, V(r) = 0 for r > a,
if it is just barely deep enough to contain one bound state.
Solution:
Concepts:
Three-dimensional square potentials
Reasoning:
We have to investigate the properties of the ground state in a three dimensional
square potential.
Details of the calculation:
If the potential only supports one bound state, this state must be an l = 0
state. The radial Schroedinger equation then is

Let
.
Rename a = r
0
.
Then from the previous problem we have |sinkr
0
| = k/k
0
, in regions where cotkr
0
<
0.
If we plot f(k) = |sinkr
0
| and g(k) = k/k
0
we find solutions at the intersections of the
two curves in regions where cotkr
0
< 0 , i.e.
.
To only support one bound state we need /2 < k
0
r
0
< 3/2,
With E near zero we have k ~ k
0
and /2 ~(2V
0
/
2
)
1/2
r
0
.
The smallest possible value for V
0
is V
0
=
2

2
/(8r
0
2
).
Problem 3:
A particle of mass m is bound in a 2-dimensional isotropic oscillator potential with a
spring constant k. Use the fact that
,
and write the Schroedinger equation for this system in both Cartesian and polar
coordinates. Separate the equation in polar coordinates and solve the resulting
equation in . Write the resulting radial equation utilizing the solution, but do not
solve it. Demonstrate the connection between the solution and its classical analog.
Solution:
Concepts:
The Schroedinger equation in polar coordinates, separation of variables
Reasoning:
We are asked to write the Schroedinger equation for the system in polar
coordinates and separate variables.
Details of the calculation:
The Schroedinger equation in Cartesian coordinates is
.
.
The Schroedinger equation in polar coordinates is
.
Let = f(r)(). Then
.
Multiply by .
.
independent of independent of r
The first term is a function of r only and the second term is a function of
only. Both terms must be equal to a constant and the sum of these constants must
be zero.

since .
The solutions are eigenfunctions of L
z
with eigenvalues n.

commutes with H, L
z
is a constant of motion, quantum mechanically as well as
classically.
The resulting radial equation is
.
.
Problem 4:
An electron in the n = 2, l = 1, m = 0 state of a hydrogen atom has a wave function
(r,,) proportional to r exp(-r/(2a
0
)) cos, where a
0
is the Bohr radius.
(a) Find the normalized wave function (r,,).
(b) Find the probability per unit length of finding the electron a distance r from the
nucleus.
(c) Find the most probable distance R
MP
of the electron from the nucleus.
(d) Find the average distance <r> from the nucleus.
Solution:
Concepts:
The fundamental assumptions of Quantum Mechanics
Reasoning:
If the wave function is normalized, then |(r,t)|
2
is the probability density.
The expression for the mean value of any observable A in the normalized state |>
is <A> = <|A|>.
Details of the calculation:
(a) Normalization:
.
.
. .
.
(b) P(r,,)d
3
r = |(r,,)|
2
d
3
r is the probability of finding the electron in an
infinitesimal volume d
3
r about r = (r,,). P(r,,) is the probability per unit
volume.

P(r) is the probability per unit length.
.
(c) We are looking for the maximum in P(r).

(d)
0.

Problem 5:
The ground state wave function for a hydrogen like atom is
,
where a
0
=
2
/(e
2
) and is the reduced mass, ~ m
e
= mass of the electron.
(a) What is the ground state wave function of tritium?
(b) What is the ground state wave function of
3
He
+
?
(c) An electron is in the ground state of tritium. A nuclear reaction instantaneously
changes the nucleus to
3
He
+
. Assume the beta particle and the neutrino are
immediately removed from the system. Calculate the probability that the electron
remains in the ground state of
3
He
+
.
Solution:
Concepts:
The hydrogenic atom, the sudden approximation
Reasoning:
Tritium and He
+
are hydrogenic atoms. Their wave functions and energy levels can
be obtained from the wave functions and energy levels of the hydrogen atom using
scaling rules. We assume that right after the decay of tritium the wave function of
the electron is the same as right before the decay. It does not have time to
change. This is the sudden approximation.
Details of the calculation:
(a) For a hydrogen atom we have
.

Defining
,
we write
.

For a hydrogenic atom we have
.

.

Defining
,
we write
.

The same equations have the same solutions. To find the eigenfunctions and
eigenvalues of the Hamiltonian of a hydrogenic atom we therefore replace in the
eigenfunctions of the Hamiltonian of the hydrogen
atom , and in the eigenvalues of the Hamiltonian of the
hydrogen atom we replace .
(a) Tritium: The reduced mass is
,
assuming the neutron mass equals the proton mass.
The nuclear charge is Z = 1. Since a
0
' ~ a
0
the ground state wave function of the
tritium is the ground state wave function of the hydrogen atom.
.
(b)
3
He
+
: The reduced mass is
,
assuming the neutron mass equals the proton mass.
The nuclear charge is Z = 2. Since a
0
' ~ a
0
/2 the ground state wave function of the
3
He
+
is
.
(c) Sudden approximation:

.
.
Problem 6:
Certain nuclei can occasionally de-excite by internal conversion, which is a process
whereby the excitation energy is transferred directly to one of the atomic electrons,
causing it to be ejected from the atom. (This process competes with de-excitation by
photon emission.) It is a reasonable assumption that the probability of this
occurrence on a particular electron is directly proportional to the probability of that
electron being at the nucleus. Of the n = 2 electrons, which are the most likely to
undergo internal conversion and why? Estimate the ratio of conversion of 1s electrons
to that of 2s electrons. Assume that the nuclear excitation energy is much greater
than the ionization energy of the 1s electron.


Solution:
Concepts:
Hydrogenic atoms, fundamental assumptions of Quantum Mechanics
Reasoning:
The probability that the electron is found at the nucleus is proportional to
|
nlm
(r=0)|
2
.
Details of the calculation:

2p
(0) = 0,
2s
(0) 0. The 2s electron is more likely to undergo internal conversion
than the 2p electron.
Ratio: (1s internal conversion)/(2s internal conversion) = |
1s
(0)|
2
/|
2s
(0)|
2
= 8.
Problem 7:
In the interstellar medium electrons may recombine with protons to form hydrogen
atoms with high principal quantum numbers. A transition between successive values
of n gives rise to a recombination line.
(a) A radio recombination line occurs at 5.425978 * 10
10
Hz for a n = 50 to n = 49
transition. Calculate the Rydberg constant for H.
(b) Compute the frequency of the H recombination line corresponding to the
transition n = 100 to n = 99.
(c) Assume the mean speed in part (b) is 10
6
m/s. At what frequency or frequencies
would the recombination line be observable?
(d) Consider that radio recombination lines may be observed at either of two
facilities, the 11 meter telescope at Kitt Peak near Tuscon, Arizona, and the 1.2
meter radio telescope at Columbia University in New York. Relative larger blocks of
time are available on the smaller telescope, but its intrinsic noise is moderately
high. Where would you choose to map recombination radiation emanating from an
external galaxy. Discuss both technical and non technical aspects of your choice.
Solution:
Concepts:
The hydrogen atom, transitions between energy levels, the Doppler shift
Reasoning:
The wavelengths of the light emitted by excited hydrogen atoms can be found using
the formula
1/ = R
H
(1/n
2
- 1/n'
2
). The observed wavelengths depend on the relative speed of
the source and the observer.
Details of the calculation:
(a) E
n'
- E
n
= h = hcR
H
(1/n
2
- 1/n'
2
).
5.425978 * 10
10
= 2.99792458 * 10
8
R
H
(1/49
2
- 1/50
2
), R
H
= 1.097373 * 10
7
m
-1
.
(b) = cR
H
(1/99
2
- 1/100
2
) = 6.679710 * 10
9
s
-1
.
(c) The line is Doppler shifted.
' = [(1 + v/c)/(1 - v/c)]
1/2
~ (1 + v/c) if v/c << 1.
Here v is the relative velocity of source and observer; v is positive if the source and
the observer approach each other, and v is negative if the source and the receiver
recede from each other.
-10
6
/(3*10
8
) < v/c < 10
6
/(3*10
8
), 6.657 * 10
9
s
-1
< ' < 6.702 * 10
9
s
-1
.
(d) Here are some factors worth considering:
The amount of radiation gathered by a telescope is proportional to the square of its
diameter D.
The smallest angle that can be resolved is approximately = /D.
(For each photon we have xp
x
~ h, x ~ D, P
x
~ h/D, = p
x
/p = hc/(Dh) =
/D.)
If you assume that the radiation has a frequency of ~ 10
-10
s
-1
, then = c/ = 3
cm. For the small telescope we therefore have = 0.03/1.2 while for the large
telescope we have = 0.03/11. It takes (11/1.2)
2
= 84 times as long to gather the
same amount of radiation with the small telescope as with the large telescope.
Problem 8:
A particle of charge -e and mass m is under the influence of two stationary heavy
nuclei, each with charge Ze positioned at z = a. We shall further assume that the
particle is spinless and non relativistic.
(a) What is the Hamiltonian and the Schroedinger equation of the system.
(b) Define the angular momentum operator along the z - direction, L
z
, and show that
its eigenvalues are good quantum numbers for all of the non-degenerate energy
eigenstates. What are the possible eigenvalues of L
z
?
(c) Define the parity operator P and show that parity is a good quantum number for
all the non-degenerate energy eigenstates. What are the possible eigenvalues of P?
(d) Define the total angular momentum operator L and show that the eigenvalues of
L
2
are not good quantum numbers for the energy eigenstates.
Solution:
Concepts:
The Schroedinger equation in three dimensions, the orbital angular momentum
operator, the parity operator
Reasoning:
We are asked to write down the Schroedinger equation for the system and to define
the orbital angular momentum operator and the parity operator. We check if the
eigenvalues of an operator are good quantum numbers by checking if the operator
commutes with H.
Details of the calculation:
(a) The Hamiltonian of the electron is
.
The Schroedinger equation is
.
In spherical coordinates we have

,
.
(b) We know [ L
2
,L
z
] = 0, therefore [ H,L
z
] = 0, since the L
2
term is the only one
with a dependence. If two operators commute, then a common eigenbasis can
be found. An eigenstate with a non-degenerate eigenvalue of H is also an
eigenstate of L
z
. The possible eigenvalues of L
z
are n where n is an integer.
(c) We define the parity operator through its action on any (r).
.
[P,L
2
] = 0, since changing to - and to + does not change L
2
.
[P,V(r)] = 0. since changing to - does not change V(r).
Therefore [P,H] = 0. As above, an eigenstate with a non-degenerate eigenvalue of
H is also an eigenstate of P. The eigenvalues of P are 1.
(d) In spherical coordinates
.
.
No common eigenbasis of L
2
and H exists.
Problem 9:
Consider a diatomic molecule consisting of two identical atoms with mass m
interacting via a potential, V(R), where R is the separation between the atoms. Near
its minimum at R
0
, the potential can be approximated by
V(R) = k(R R
0
)
2
.
Write down the energies of the low lying states of the diatomic molecule, assuming
that these are rotational and/or vibrational excitations. Define the moment of inertia
of the diatomic molecule about the symmetry axis to be I
z
, and give your answer in
terms of m, I
z
, and the parameters appearing in the potential. Make sure you specify
allowed values of all quantum numbers appearing in your answer.
Solution:
Concepts:
The time-independent Schroedinger equation for two interacting particles
Reasoning:
Let r = R R
0
, r
2
= (R R
0
)
2
, V(R) = kr
2
.
If the mutual interaction depends only on the distance r between the particles,
then the eigenvalue equation for the relative motion becomes
-(
2
/(2))
2
r
(r) + V(r)(r) = E
r
f(r),
with being the reduced mass, = m
1
m
2
/(m
1
+ m
2
) = m/2.
Here -(
2
/(2))
2
r
(r) + kr
2
(r) = E
r
(r).
Details of the calculation:
Let us first consider only small amplitude vibrations.
If the angular momentum of the nuclei is zero, then the eigenvalue equation
reduces to the radial equation with l = 0,
[-(
2
/(2))(
2
/r
2
) + kr
2
]u(r) = Eu(r).
This is the eigenvalue equation of a one-dimensional harmonic oscillator
Hamiltonian. The eigenvalues are
E
n
= (n + 1/2), n = 0, 1, 2, ...,
2
= k/m,
These are the eigenenergies of the vibrational motion of the two nuclei .
[Typical vibrational frequencies are on the order of 10
12
to 10
14
Hz and fall in the
infrared.]
Let us now study the rotational motion of molecules. We neglect vibrations and
assume that the distance r between the nuclei remains constant. We then have a
rigid rotator. We have
H = L
2
/(2r
2
) = L
2
/(2I
z
), I
z
= m
1
r
1
2
+ m
2
r
2
2
= r
2
.
The eigenfunctions of H are the eigenfunctions of L
2
.
These are the spherical harmonics, Y
lm
(,). The eigenvalues are E
l
= l(l+1)
2
/2I
z
.
[Remarks:
It is customary to set B = /(4I
z
), and write E
l
= Bhl(l+1). The separation between
adjacent levels is
E
l
- E
l-1
= Bh(l(l+1) - (l-1)l] = 2Bhl. It increases linear with l. Each energy
eigenvalue E
l
is (2l+1) fold degenerate.

Pure rotational spectra fall in the very far infrared or the microwave region.]

For the vibrational and rotational motion we have for small amplitude oscillations
(so that we can neglect the change in the moment of inertia)
E
nl
= (n + 1/2) + l(l+1)
2
/2I
z
.
Problem 10:
Find the momentum space wave function (p) for the electron in the 1s state of the
hydrogen atom.
Solution:
Concepts:
Change of representation, the Fourier transform
Reasoning:
We are asked to change from the r to the p representation.
(r) = (2p)
-3/2

-
+
d
3
p (p)exp(i(p/)r),
(p) = (2p)
-3/2

-
+
d
3
r (r)exp(-i(p/)r),
(r) and (p) are Fourier transforms of each other.
Details of the calculation:
The 1s wave function is
.
Therefore
.
Symmetry demands that (p) = (p).
Let us choose a convenient direction for p. Let p = pk. Then



.
.