Recommended problems and optional hand-ins in

Atomic Physics spring 2018.

Lars Engström

The recommended problems below will help you understand the theory, train your problem-
solving skills as well as giving you a very important working knowledge of atomic physics.
I strongly suggest that you do all (most of) these problems in the given order, since this will
also prepare you for the hand-ins.
The problems marked as hand-in are problems that you may solve and hand in to obtain
credits on the first and second examination opportunity. The exam will consist of 6 problems
giving at most 4 points each, i.e. a maximum of 24. A passing grade will require 12 and “väl
godkänd” 19 points. Solving perfectly all optional hand-in problems will give you 3 + 3 = 6
points on the exam. The deadline for the first hand-in is Monday 29/1 and for the second
Monday 5/3.
Rules and regulations regarding the hand-ins
 The hand-ins must be solved in groups of 2 students (registered for the first time on
the course), no more and no less!
 The problems give different points and you may do any number of them but at least
two in each hand-in.
 Each problem must be solved on a separate paper.
 The complete hand-in should be stapled together, with a cover page containing your
names, e-mail and personal identification number.
 In addition to a correct solution it is required that you write carefully in a clear and
pedagogical manner. Every numerical answer must have the appropriate unit.
 All diagrams must have descriptive captions and axis labels with the appropriate
units.
 It is allowed and encouraged that you discuss the physics in general with other
students, but it is absolutely essential that each group individually solves the actual
problems and writes the report. Note that, if you do them, the hand-ins are part of the
exam and all official rules conserning plagiarism, with severe possible repercussions,
applies.

1. The wavenumber for a transition between two levels is 50000 cm-1.

a) What is the wavenumber in the unit 1 m-1?
b) What is the wavelength of the transition?
c) What is the energy difference in the unit 1 eV?
d) How many cm-1 is 1 eV?

2. Show that a small increase in the energy of a level in an atom results in a decrease of the
same relative size in the transition wavelength, i.e. show that:
E 

E 
3. Hand-in 1 (0.5 point)
The figure shows a 4-level system starting from the ground
state. Assume the following wavelengths, in Å, and their
estimated uncertainties (one standard deviation).
λ1 = 2500 ± 0.5, λ2 = 2000 ± 0.2 and λ3 = 4000 ± 1. Derive
the energy, in cm-1, of all levels and the wavelength λ4.
Include an estimated one standard deviation uncertainty in
all the quantities. Assume all uncertainties to be
independent. (If needed, you may download from the home
page a short document (in Swedish) describing the
handling of uncertainties in experimental data.)
4. Bohr’s theory of the H-atom.
a) Show that the energy of transitions between two shells
with principal quantum numbers n and n’= n + 1 is proportional to n-3, for large
values of n.
b) Calculate the frequency of the n = 50 – 51 transition.
c) What is the size of an H-atom in the n = 50 shell?
d) Treat the electron as a classical particle and calculate the rotation frequency of the
electron in the n = 50 shell. Compare your result with 4b
5. What is the shortest and longest wavelength, respectively, that can be emitted from an H-
atom?
6. The table gives observed wavelength (in standard air with a refractive index of about
1.0003) from H and He+, respectively. Explain the data, particularly which transitions
these wavelengths correspond to?
Wavelength / nm

H 656.28 486.13 434.05 410.17

He+ 656.01 541.16 485.93 454.16 433.87

7. Commutator relations.
a) Prove one of these important commutator relations
 Lˆx , Lˆ y   i Lˆz ,  Lˆ y , Lˆz   i Lˆx ,  Lˆz , Lˆx   i Lˆ y
     
b) Prove that  Lˆ2 , Lˆi   0, i = x, y or z.

8. Hand-in 1 (0.5 point)

A particle is described by the wavefunction :
1
( , )  (Y1,1  2Y2,1 ), where Y ,m is an orthonormal spherical harmonics.
5
a) Is this an eigenfunction of Lˆz ? If so, what is the eigenvalue?
b) Is this an eigenfunction of Lˆ2? If so, what is the eigenvalue?
c) What is the expectation value of Lˆz in the state described by ?
d) What is the expectation value of Lˆ2 in the state described by ?
9. Use a table or the net to look up all spherical harmonics with ℓ = 0, 1 and 2 and motivate,
by direct calculation, the general result that for each ℓ-value the sum over all possible m-
values is spherically symmetric, i.e. show that:
2 1

2
Y ,m ( ,  )  , independent of the angles.
m  4
This statement, called Unsöld's theorem, shows that filled orbitals are spherically
symmetric, and hence contributes nothing to the angular momentum couplings.

10. Hand-in 1 (0.5 point)

For two electrons we have s1 = 1/2 and s2 = 1/2. Make a table of all possible z-
components that arise when the angular momentum (vectors) s1 and s2 are added. Show
that this exactly corresponds to the components you would get from a quantized
momentum (vector) S = s1 + s2 with the quantum number S = 0 and 1.

11. Let Y i ,mi be an eigenfunction of ˆ 2i and ˆ zi for i  1, 2 in a two electron atom. The total
orbital angular momentum is given by L̂  ˆ 1  ˆ 2 and the eigenfunction of Lˆ2 and Lˆz ,
 1 , 2 , L, M
, can be expressed as linear combinations of those for the individual angular
momenta, Y i ,mi , using the Clebsch-Gordan coefficients, C.
 1 , 2 , L,M
  C ( 1 , m1 , 2, M  m1 : L, M )  Y 1 ,m1  Y 2 ,M m1
m1

a) Make a table of all possible combinations of m 1 , m 2 and the resulting

M L  m 1  m 2 when we couple a p and a d-electron. How many combinations give
M L = 1 and how many give M L = 2? Which L-values are involved in these states?
b) Write down the complete wavefunctions corresponding to these L-values and
M L = 1 and 2. Use, for example, the Clebsch-Gordan calculator found at:
http://personal.ph.surrey.ac.uk/~phs3ps/cgjava.html to obtain the analytical values
of the Clebsch-Gordan coefficients. For clarity, use the notation Y i ,mi to denote the
spherical harmonics, do not write them out explicitly
c) Chose one of the M L = 1 functions and show that it is normalized and orthogonal to
all the others with M L = 1. Use the relation Y ,m Y ',m '   , '   m ,m '

12. The radial wavefunctions, Rnl(r), for a one-electron system with nuclear charge Z and
n = 3 are:
2Zr 2( Zr ) 2  Zr / 3
R30 (r )  2( Z / 3)3 / 2  (1   )e
3 27
4 2 Zr
R31 (r )  ( Z / 3)3 / 2  (1  )  Zre  Zr / 3
9 6
4
R32 (r )  ( Z / 3)3 / 2  ( Zr ) 2  e  Zr / 3
27 10
where the distance, r, from the nucleus is measured in the unit 1 a0.
a) Use e.g. MatLab and plot the functions for Z = 1 and Z = 2. What happens as Z
increases?
b) Which orbital is 0 at the nucleus, r = 0?
c) Verify that the number of nodes, i.e. zero-crossings, for r > 0 is given by n - l – 1.
13. Hand-in 1 (0.5 point)
The probability of finding the electron at a distance r, independent of the angles θ and φ,
is given by the radial distribution function Dn ( r ) .
2
Dn (r )  r 2 Rn (r )
a) Plot Dn ( r ) for Z = 2 for the 3s, 3p and 3d orbitals above.
b) Use the figures to estimate the distance corresponding to the maximum probability
for 3d and compare with the value calculated using the Bohr formalism.

14. Hand-in 1 (0.5 point)

In quantum mechanics the mean radius (in units of 1 a0) is calculated as the expectation
value:

 r n   Rn*  r Rn  r 2 dr
0

Use e.g. MatLab to numerically calculate < r > for the 3 orbitals above for Z = 2 and
1
compare with the general quantum mechanical expression.  r n  [3n2  (  1)]
2Z
15. In Hydrogen the complete wavefunction for the ground state is:

1
1s (r , ,  )   e r / a0
 a0
3

Calculate analytically the probability of finding the electron inside a sphere of radius rb
centered on the nucleus. Assume rb << a0 so that you may make convenient
approximations.

16. Calculate the internal magnetic field experienced by a 2s and a 2p-electron in He+ and in
F8+. Use the general quantum mechanical result for a one-electron system

1 1 Z 3
 n  ( ) , 0
r 3
(  1/ 2)(  1) na0

17. Motivate the selection rule j = 0, 1, not 0  0. Assume that the atom makes a
transition from a level with j = 3/2 to a lower level j' through the emission of a photon
with spin s = 1. Calculate all possible z-components that arise when the angular
momenta (vectors) j and sare subtracted. Show that this exactly corresponds to the
components from a quantized momentum (vector) j’ with the quantum number j =1/2,
3/2 or 5/2.

18. Calculate the wavelengths for 1s 2S1/2 – 2p 2P1/2,3/2 in He II including the 3 relativistic
corrections (mass, spin-orbit and Darwin). Compare with the accurate experimental
results available in the data base at NIST (National Institute of Standards and
Technology) in Washington, USA http://physics.nist.gov/PhysRefData/Elements/
index.html. (Click on the element symbol in the periodic table, then choose ”Lines” among the
database icons that appear.) Which effect is responsible for the small, but significant,
remaining discrepancy in the absolute energies?
19. The configuration 1s23d in Li I has the (excitation) energy 31283.10 cm-1. The ionization
energy in Li is 43487.19 cm-1.
a) What is the term value of the ground state 1s22s?
b) What is the binding energy of 1s22s?
c) What is the term value of 1s23d?
d) What is the term value of 3d in H?
20. In He I there is a state with the energy 166271 cm-1 and the term value 32034 cm-1. What
is the ionization energy?
21. Use the database at NIST (National Institute of Standards and Technology) in
Washington, USA http://physics.nist.gov/PhysRefData/Elements/index.html to obtain
level energies in F VII and the ionization limit for F+6
(Click on the element symbol in the periodic table, then choose ”Levels” among the database
icons that appear. For the ionization limit, scroll down the NIST table!)
a) Calculate the term value of 1s23s.
b) Calculate the quantum defect for the 4s, 4p, 4d and 4f states. Use the center-of-
gravity energies (2j+1 weighted mean) for the 4p 2P and 4d 2D terms.

22. In He-like Carbon, C V, the excitation energy of 1s3s 1S is 2851180 cm-1 and for 1s4s 1S
it is 2988246 cm-1. Estimate the ionization energy. Compare with the value in the NIST
database!

23. Hand-in 1 (0.5 point)

The spectrum shows the series
3p - nd, n = 4 - 7 in Na as well
as the resonance line 3s - 3p,
with the experimental vacuum
wavelengths in Å.

a) Why does the 3p - 5s

transition (6160 Å) occur
at a much longer
wavelength than 3p-5d?
b) Calculate the quantum
defect for the nd 2D
n = 4-7 terms. Estimate, as
accurately as possible, the wavelength for 3p - 8d. The ionization energy in Na I is
41449.6 cm-1. Neglect all finestructure.
24. Ionization energy in He-like C, C V.
An accurate experimental value is (3162408 ± 20) cm-1.
a) Estimate the ionization energy by completely neglecting the repulsion between the
electrons.
b) Now refine your value by making a semi-classical estimate of the repulsion energy
by simply assuming that the two electrons always are on the opposite side of the
nucleus from each other, i.e. separated by the diameter of the first Bohr orbital.
c) Use first order perturbation theory to calculate the ionization energy in C+4. Note
that the repulsion energy, to first order, is a linear function of Z given by
Erep  1.25  R  Z for 1s2 in a two electron system, see e.g. AP eq. 3.24.
25. Hand-in 2 (1 point)
Derive the electrostatic repulsion potential felt by an outer electron in Li, e.g. a 4f
electron being attracted to the nucleus and repelled by the two inner 1s electrons.
a) Write down the total charge density of the two 1s electrons, i.e.
 (r )  2  e  100 ( r, , )
2

Here we rather crudely assume that both electrons move independently and feel the
full charge, +3e, from the nucleus.
b) To obtain the corresponding electrostatic potential you have to solve Poisson's
equation:
1 d2
2V ( r )    ( r ) /  0  ( rV ( r ))    ( r ) /  0 .
r dr 2
Where we have used the radial part of 2 in polar coordinates, as we did when
solving the one-electron problem. Derive V(r) by direct integration. This requires
some partial integrations and a bit of work!
Hint: Introduce new help variables to get nice looking equations without any
explicit fundamental constants and do not forget the integration constants. Use
reasonable boundary conditions (at r = 0 and r = ∞) to determine the integration
constants.
c) Plot the final repulsion energy U (r )  e V (r ) , the Coulomb energy from the
nucleus, and the sum in the same plot frame. Use eV as the energy unit and a0 as the
unit for distance.

26. The table gives the energies in the 3s3p configuration in Mg I and in Mg-like Fe XV.
a) Give the LSJ-designations for the levels.
b) Is the Landé interval rule valid in the two atoms?
c) A line at 417.26 Å in the solar spectrum has been
identified as emanating from the 3s3p configuration in
Fe XV. Which transition is it? Would you expect an
analogous line in Mg I?

27. Prove that the number of fine structure levels in an LS-term is Min(2S  1, 2L  1).

28. sp – pp’ transitions.

a) What LSJ-levels do these configurations give rise to?
b) Which transitions are (LS) allowed between these configurations?

29. Hand-in 2 (0.5 point)

p2 – pd transitions.
a) What LSJ-levels do these configurations give rise to?
b) Which transitions are allowed between these configurations in LS-coupling?
30. The table below gives J-values and energies for the levels in the 3p4s and 3p7s configu-
rations of Si I.
E / cm-1
J 3p4s 3p7s
0 39683.163 61538.05
1 39760.285 61595.43
2 39955.053 61823.55
1 40991.884 61881.60

a) Give the LS-designation for the levels.

b) Why do the two configurations have nearly the same ∆E (2 - 0) but quite different
∆E (1 - 1)?
c) Give the jj-designation for the levels in 3p7s.

31. Hand-in 2 (0.5 point)

The table gives the theoretical relative intensities in
LS-coupling for all possible 3F – 3G transitions.
a) Use this data to verify the sum rules for
LS-intensities in a multiplet.
b) Use the sum rules to derive the relative intensities in a 2D – 2F multiplet.
Hint: denote the intensities a, b and c and solve a system of equations.
32. Zeeman effect in Na.
a) Calculate the g J -value for the levels 2S1/2, 2P1/2, 2P3/2.
b) Derive the splitting of the 2S1/2 - 2P3/2 line in a weak magnetic field when viewed
perpendicular to the field.
c) What is the polarization of the different components?
d) What is the spacing, in units of 1 cm-1 and in 1 eV, between the closest-lying
components if the magnetic field is 1 T?
e) Look up the wavelengths of the two fine structure lines 3s – 3p in Na I. What
magnetic field would produce a Zeeman splitting, as in 32d), equal to the energy
difference between these lines?

33 Zeeman vs. Paschen-Back effect.

With a weak magnetic field we first couple L and S to J and use │LSJMJ > coupled
wavefunctions to calculate the magnetic contribution as a perturbation. If, on the other
hand, the external magnetic field becomes sufficiently strong (e.g. in a white dwarf star)
the order should be reversed, i.e. we first evaluate the magnetic interaction using the
wavefunctions │LMLSMS > (which is much easier) and then take the spin-orbit
interaction <βL·S> = β·<Lz·Sz> into account. Make a clear and easily understandable
table of the energies, and draw an energy diagram showing the splittings of a 3P term in
1
the 2 cases: Zeeman:  B B   , and Paschen-Back: B B  10 . (Strictly, the factor
10
should be larger than 10 for the perfect extreme cases, but then it will be difficult to draw
nice diagrams!)
34. Hand-in 2 (0.5 point)
Line widths in wavelength units.
a) The 3p level in Na I has a lifetime of about 16 ns. Calculate the natural line width
(in Å) of the 3s – 3p transition at 5890 Å.
b) If the Na-atoms are created in an oven with a temperature of 700 K what is the
Doppler width of the 5890 Å transition.
c) Assume the spectrum is analyzed in the first spectral order using a 5 cm wide
grating with 2400 lines/mm. What is the smallest possible observed line width? (In
practice it will most likely be much larger!)
d) In the spectrum of He there is a line at 2578 Å that corresponds to the transition
2s2p 3P – 2p3p 3D, i.e. a transition between two doubly excited configurations. The
excitation of both electrons in He requires so much energy that these configurations
are situated above the first ionization limit. This also means that the states have a
probability to decay through the emission of an electron, so called autoionization. If
possible, this process is very probable and leads to very short lifetimes. Assume that
both terms have a lifetime of 1 ps and calculate the natural line width of the 2578 Å
transition.

35. The figure below shows the hyperfine structure in the transition 6s 2S1/2 - 8p 2P3/2 in 115In
(I = 9/2). The measurement is made using a narrow-band tunable laser and a collimated
atomic beam; hence the Doppler width is greatly reduced. The 6 components shown
have the following frequencies 31, 112, 210, 8450, 8515 and 8596 MHz. Draw a
schematic figure of the energy levels with the appropriate quantum numbers and show
the allowed transitions. Determine the hyperfine constants, in MHz, for the two fine
structure levels
36. A high-resolution scan over the resonance line 4s 2S1/2 - 4p 2P1/2 in K I is shown in the
figure below, where the relative positions and intensities of the observed hyperfine
components are given. Naturally-occurring potassium is a mixture of the isotopes 39K
and 41K in the ratio 14:1. Identify the lines in the figure and deduce the nuclear spin of
the two isotopes.

37. The observed spectrum of F6+ (F VII) contains, among many other lines, the following
wavelengths with their estimated relative intensities corresponding to transitions among
levels with n 3. The intensities are not calibrated, and can hence only be compared
between closely spaced lines. Use this data to derive the energies (in cm-1) for all
observed levels with n  3 in F VII.
λvac / Å Rel. Int.
112.941 806
112.977 410
127.653 950
127.799 1600
134.707 430
134.882 870
883.11 1700
890.79 800
3247.48 130
3277.90 60

Hint: Start by drawing a term diagram with roughly the correct relative energies of all
the possible terms 1s2nl with n  3 and indicate their fine structure levels. Then solve the
“puzzle”, making good use of the relative intensities. The better your relative energies
are the easier it will be to solve the problem. Check as much as you can that the solution
is consistent.
38. The Ca spectrum below, recorded using a Fourier Transform Spectrometer (FTS), shows
the resolved 3d4s 3D - 3d4p 3D multiplet. The wavenumbers and their relative intensities
are given in the table. Identify all the lines and determine the fine structure constants in
the two triplets (both are positive).

σ / cm-1 Rel. Int.

17841.88 106
17847.70 101
17856.50 353
17869.12 414
17883.32 250
17887.54 1074
17909.46 160

39. We are investigating hydrogen in a plasma with the temperature 4500 ºC. Calculate the
probability per atom and second for stimulated emission from 2p to 1s if the lifetime of
2p is 1.6 ns

40. A classical model for the vibration of the Oxygen- and Carbon-atom in a CO molecule
can be obtained as follows. The potential energy of the binding force between the atoms,
as a function of their separation, r, is quite accurately given by the Morse potential:
U (r )  D  (e2a( r r0 )  2e a( r r0 ) ).
Here D = 11.36 eV is the binding energy. The equilibrium distance between the atoms is
r0 = 1.15 Å and the empirical constant a = 2.29 Å-1 for CO.
a) Draw a diagram of the Morse potential between e.g. 0.8  r  5 Å.
b) Assume that the kinetic energy due to the vibration is 9.36 eV. What is then the
smallest and largest possible separation between the atoms in a classical picture?
c) To simplify the calculations we approximate the Morse potential by a harmonic
oscillator. This approximation should be quite accurate if we are close to the
minimum in the real potential (r ≈ r0). Calculate a number of values for the Morse
potential very close to r0 and fit a second order polynomial to the data. Draw the
polynomial in the same figure as in a). In what range would you say that the
approximation is reasonable?
d) Use the general expression
dU
F 
dr
to show that the ”spring constant” [k in the expression for the force in a harmonic
oscillator F  k  (r  r0 ) ] is twice the coefficient for the second order term in the
polynomial approximation.
 e) Use your value of k together with the reduced mass μ of the CO-molecule to
calculate the vibrational frequency from the harmonic oscillator model:
k
0  .

Compare with the experimental result ω0 = 3.97·1014 rad/s => f = 6.32·1013 Hz.
Hint: make sure that you get the unit of k correct for this calculation.

41. The rotation fine structure in the n = 0 - n = 1 vibration transition in HCl is shown in the
figure. The wavenumbers for the 4 central lines are given in the table. Chlorine has two
isotopes 35Cl (76%) and 37Cl (24%), with mass 34.968852 and 36.965903 u,
respectively. Use the data in the table to:
a) Determine the equilibrium
distance between the H and Cl
atoms in the two isotopes.
b) Determine the resonance
frequency for the vibration of
the atoms in the two isotopes.
σ / cm-1 Rel. Int.
2862.8404 216
2864.9120 511
2903.9340 231
2906.0693 532

42. Hand-in 2 (0.5 point)

The wavenumbers for the first 3 members of the R and P branch in the 0 - 2 vibrational
transition in CO are given in the Table below.

Wavenumbers of the R and P branch in CO

σ / cm-1
4248.13
4252.13
4256.06
4263.65
4267.37
4271.01

a) Determine the energy difference between the vibrational levels 0 and 2 and the
rotation constant, B, (in the unit 1 cm-1) assuming that the moment of inertia is the
same in both states.
b) Repeat the analysis but this time take into account that the rotation constants,
B'' (ν = 0) and B' (ν = 2) are not exactly equal.
43. The lines in the table below are identified as transitions to a quartet P from two higher-
lying quartets (S and D) in F V. 4P - 4S have wavelengths around 2250 Å while the 4P -
4
D transitions occur around 2700 Å. All possible transitions in the latter multiplet, shown
in the figure, could not be resolved in the experiment. Identify all the lines!

λvac / Å Rel. Int.

2241.14 320
2253.75 610
2277.73 820
2703.10 710
2707.97 990
2713.68 200
2721.87 270
2737.72 240
2756.99 50

Hint: All the terms involved have a positive fine-structure constant. Furthermore, in pure
LS-coupling the relative intensities in a 4P - 4D multiplet is given in the table below.
Even if a real term system is not perfectly described in LS-coupling these relative
intensities is often of great qualitative help.
4
D
7/2 5/2 3/2 1/2
5/2 120 27 3
4
P 3/2 63 32 5
1/2 25 25
44. In the Zeeman laboratory exercise you study the multiplet 5s5p 3P - 5s6s 3S in Cd I in a
magnetic field. Here we investigate another multiplet in Cd, with no external field. The
figure below shows the observed 5s5p 3P - 5s5d 3D multiplet, where the inset gives a
magnified picture of the three rightmost lines.

Table 1 list the wavelengths and relative intensities obtained in the spectrum and Table 2
gives the experimental energies for the 3P levels.

Table 1. Table 2

λvac / nm Relative Intensity 5s5p3PJ E / cm-1

340.4629 2183 0 30113.99
346.7193 3363 1 30656.09
346.8648 2566 2 31826.95
361.1538 4824
361.3903 2615
361.5484 389

a) Identify the six transitions.

b) Derive the energies of the 3D levels, as accurately as possible from the given data.
c) Check the Landé interval rule in both 3P and 3D. Is this consistent with LS-
coupling? If not, what could be the reason(s)?
d) Check the sum rules using the experimental intensities. Is this consistent with LS-
coupling? If not, what could be the reason(s)?
e) The barely noticeable peak at 350 nm is the so-called forbidden transition 5s5p 3P1 -
5s5d 1D2. How does such a line arise?