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4 Bohr Model - Lecture notes 4

Matter: Evidence for Quant (Nottingham Trent University)

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4.0 The Bohr Model of the Hydrogen Atom

4.1 Rutherford’s Model


In Rutherford’s model of the hydrogen atom, a negatively charged electron orbits the positively
charged nucleus. The problem with this model is that the orbiting electron must accelerate in order to
maintain its circular path, but accelerating charges emit electromagnetic energy, so the electron must
lose energy. Loss of energy will cause the orbital radius to decrease, and hence the acceleration to
increase, until eventually the electron spirals into the nucleus.
Predicted consequences:
• Atoms should be unstable
• Atoms should emit light continuously and with increasing frequency (continuous spectra).
Observations:
• Atoms are stable
• Atoms emit light at discrete frequencies (line spectra)

Thus the Rutherford model contradicts experimental observation.

4.2 Bohr’s Postulates


In 1913 Bohr modified the Rutherford model of the hydrogen atom by adding some
assumptions/restrictions, in the form of four postulates, and as a consequence was able to derive
Balmer’s formula for the line spectra of hydrogen.

Postulate 1:
The electron in the hydrogen atom moves in circular orbits centred on the nucleus.
In hydrogen, the nucleus is simply a proton, and the force between the electron and the proton is an
attractive electrostatic force given by Coulomb’s law.
 e2
F
4 0 r 2
Note: Model assumes a massive stationary nucleus.

Recall:
• A particle of mass m and velocity v in a circular orbit of radius r has an angular momentum
defined by L=mvr
• In classical mechanics all values of angular momentum are allowed.

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Postulate 2:
Quantisation of angular momentum.
Newton’s laws of motion apply, but angular momentum L is quantised, i.e. the angular momentum can
take only certain specific values.
h h
L me vr n n n 1, 2, ... define  
2 2
n = 1, 2, 3…is the Bohr quantum number (a positive integer number)
h = 6.6.3´¼10-34 J s is Planck’s constant; me is the mass of an electron.

Postulate 3:
The electron moves in stable orbits without emitting electromagnetic radiation, in contradiction to
classical physics. Each stable orbit corresponds to a bound state of the atom and has a well defined
energy.
 No continuous emission of electromagnetic radiation for the electron in stable orbits
 electron does not loose energy gradually
 total energy of electron is constant in each of the stable orbits.

Postulate 4:
Atom radiates energy - a photon - if and only if it makes a transition from one stable orbit of Energy Ei
to another stable orbit of energy Ef.
This provides a link between atomic structure and electromagnetic radiation, explaining the line
spectra of atoms.

Bohr Frequency rule (applies to all atoms):


• A photon is absorbed if and only if its energy equals the energy difference between two stable
orbits.
E  Ei
Ei  hn E f  n  f
h
• A photon is emitted when a transition occurs from a higher energy orbit to a lower energy orbit.
E  Ef
Ei  E f hn  n  i
h
• In general, for emission/absorption, the frequency of radiation n:

Ei  E f
Ei  E f hn  n 
h

Ei > Ef for emission


Ei < Ef for absorption

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Absorption

Emission

4.3 Allowed Bohr Orbits


There are two forces on the electron orbiting the nucleus of the H atom:
Electrostatic force: e2 Centripetal force: me v 2
4 0 r 2 r
Balancing the centripetal force with the electrostatic force: me v 2 e2

r 4 0 r 2

Now, angular momentum is quantised, so: L me vr n n 1, 2,3...


n
 v
me r

Substituting this expression for angular momentum into the force balance equation:
2
me  n  e2
  
r  me r  4 0 r 2
Solving for r:  4 0  2  2
r  2 
n
 me e 
  0 h2  2
r  2 
n a0 n 2 n 1, 2,3....
  me e 

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So the allowed radii of the circular orbits are given by:

 r rn a0 n 2 n 1,2,3....

 0h 2 
where a0  0 . 53 A
 mee 2

a0 is a constant known as the Bohr radius.


Allowed radii can only take the specific values given by the above equation  they are quantised
e.g.: for n=1, r1 = a0 = 0.53 so a0 is the radius of the first allowed orbit
for n=2, r2 = 22 a0 = 4a0 etc.

Allowed electron velocities:


Substituting this new expression for r back into the earlier equation for velocity gives
n n
v 
me r me a0 n 2

Using the definition of a0 also gives:


e2  1 
v v n    n 1, 2, 3...
2 0 h  n 

 the speed of the electron is also quantised and is  1/n.


• Speed is largest when n is smallest (i.e. n=1).
• When n is very large, v is small, hence KE®0
• n large means r is very large  Electrostatic force is negligible Electron free from the atom
and can be at rest, hence its KE®0.

Allowed Energies:
2
• Kinetic energy K is quantised: 1 1  e2  me e 4  1 
K  me v  me 
2
  2 2 2
2 2  2 0 hn  8 0 h  n 
• Potential energy U is quantised:
e2 e 2  mee 2  mee 4  1 
U        
4 0 r 4 0   0 h 2 n 2  4 02 h 2  n 2 
• Total energy E=K+U is quantised:
me e4  1  mee 4  1  mee 4  1 
En  2 2  2      2 2  2   2 K
8 0 h  n  4 02 h 2  n 2  8 0 h  n 

mee 4  1  E1  13.6 
Allowed energies En  2 2 2
 2   2  eV
8 0 h  n  n  n 

me e 4  1 
where E1  2 2  2 
 2.176 ´10 18 J  13.6 eV
8 0 h  1 
Note especially:
• The allowed energies are quantised and are 1/n2.
• Potential energies are negative because the potential energy is taken to be zero at infinity and the
mutual attraction between the two charges gets larger the closer together they get.
• As nincreases, the energy states become closer together, since
1 1 1 1 1 1
2
® 1, , , , , ...
n 4 9 16 25 36

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Energy level diagram for atomic hydrogen, extended to include the continuum.

Discussion of results:
• Bound states always have a total energy that is negative.
• The lowest possible energy state of an atom is known as its ground state. For the hydrogen atom
this corresponds to -13.6 eV (n=1).
• Atoms remain in their ground state unless energy is supplied to them.
• States of higher energies than the ground state are referred to as the corresponding excited states.
For hydrogen, these correspond to n>1 (2,3..).
• Normally, an electron in an excited bound state “decays” back to the ground state at some later
time via the emission of a photon.
• To remove an electron from an atom, energy has to be supplied. Once this has been accomplished,
a positively charged ion is left behind. The atom is then said to have been ionised.
• The minimum energy required to remove a ground state electron (n=1) to an infinitely large orbit
(n=¥) is called the ionisation energy or the ionisation potential of the atom. e.g. using the
equation for the allowed energies it follows that the ionisation energy for hydrogen is 13.6 eV.
This minimum energy will leave the electron at rest at infinity.
• If the electron is given more energy than the minimum required for it to reach the ionisation level
then it will escape from the nucleus and move freely with a velocity v. Since its potential energy is
zero once it is outside the influence of the nucleus, the electron is said to be in an unbound state.
The characteristics of an unbound state are that U=0 and K>0, so its total energy is positive: an
electron in an unbound state can have any positive energy, in contrast to the quantised bound state
energies. Unbound electron states are said to be lying in the continuum.

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Example 1: What are the energies of the first and second excited states of the H atom?
Answer: En = - 13.6 / n2 eV
 E2 (1st excited state) = - 13.6 / 22 = - 3.4 eV.
 E3 (2nd excited state) = - 13.6 / 32 = - 1.5 eV.

Example 2: What would happen if 4eV of energy is supplied to an electron in the n=2 state in a
hydrogen atom?
13.6
Answer: Energy of n=2 orbit, E2  2 eV  3.4 eV
2
If 4 eV supplied to electron then total energy of electron becomes -3.4 eV+4 eV = 0.6 eV > 0.
This would put electron into the continuum, with a kinetic energy of 0.6 eV.
Speed of electron can be deduced:
1 2K 2 ´0.6 ´1.602 ´10  19
K  mv 2  v    31
~ 4.6 ´105 m / s
2 m 9.11 ´10

Practice Question - Section 4.3


Try to answer this question yourself, before checking your work against the model answer provided at
the end of this document.
1. The radius of the Bohr orbit for an electron in the ground state of hydrogen is 0.53 Å. What is it for
the third excited state ?

4.4 Energy Level Transitions and Line Spectra

(a) Emission: Electron makes a transition from higher energy state (n=ni) to a lower energy level
(n=nf) by emitting a photon. (ni>nf)
(b) Absorption: Electron absorbs sufficient energy from the incident photon to move to a higher
energy level (ni<nf).
The energy of the light photon must match the energy difference between the energy levels of the two
states involved in the transition.

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Recalling the Bohr Frequency rule for the emission or absorption of radiation:

Ei  E f
n
h
(where for emission ni>nf and for absorption ni<nf)

and substituting for Ei & Ef from the allowed energies formula:


1 me e4 1 1
n  2
h 8 0 h ni n f
2 2 2

mee 4 1 1 1 1
 2 3 2  2 RH c 2  2
8 0 h n f ni n f ni

me e 4
where RH  1.09737 ´107 m  1
8c 0 h
2 3

and RH is Rydberg’s Constant.

This is the same equation as that obtained in the section on spectra, and it explains the empirical
formula of the line spectra of Hydrogen.

Alternatively, it can be written in terms of wavelengths of emission, l=c/n:


c 1 1 1 1 1
RH c 2  2  RH 2  2
l n f ni l n f ni

The total energy of the atom can thus be expressed in terms of RH as:
 1 
En  RH hc  2  , n 1, 2, 3...
n 

Emission spectra of hydrogen


• Lyman series: transitions to n=1
• Balmer series: transition to n=2
• Paschen series: transition to n=3
• Brackett series: transition to n=4
• Pfund series: transition to n=5.

So the Bohr model explains the line spectra and energy levels of hydrogen.

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Example: An electron is in its lowest energy state. What would happen if:
(a) a photon of 10.2 eV is incident on the atom ?
(b) a photon of 10 eV is incident on the atom ?
Answer: Lowest energy state  n=1 and E1= -13.6 eV
(a) 10.4 eV supplied, total energy of electron would be -13.6 +10.2 eV = -3.4 eV
-3.4 eV = -13.6/4 which corresponds to the n=2 level of Hydrogen.
In other words, the photon matches the energy difference between the n=2 and the n=1 bound states, so
the electron absorbs the photon and makes the transition from the n=1 to the n=2 orbit.
(b) Photon with energy 10 eV
Total energy of electron would be:
-13.6 +10.0 eV = -3.6 eV
-3.6 eV does not correspond to a bound state of the atom, so nothing happens and electron does not
absorb the photon.

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Practice Questions - Section 4.4


Try to answer these questions yourself, before checking your work against the model answers provided
at the end of this document.
2. Find the wavelength of the photon emitted when a hydrogen atom goes from the n=10 excited state
to its ground state.
3. If a hydrogen atom is in its first excited state, what is the energy and wavelength of the photon it
needed to remove the electron from the atom?
4. In 1908 Friedrich Paschen observed two infrared lines with wavelengths 1875.1 nm and 1281.8 nm
in the emission spectra from hydrogen. Using Bohr’s model we can work out that these are
transitions to the n=3 level. Work out what levels they come from.
5. If a hydrogen atom is in its sixth (n=7) excited state, what is the longest wavelength photon it can
emit and what is the longest wavelength it can absorb before being ionized?

4.5 Thermal Energy & Excitation


Atoms remain in their ground state unless energy is transferred to them from some external source: this
process of energy transfer is known as excitation (e.g. by light). Atoms can also receive energy by
thermal excitation through collisions between atoms (or from atoms).

Franck-Hertz experiment (1914):


This provided the first experimental evidence for the existence of atomic energy levels. In the
experiment, a current is passed through a cylinder filled with a gas (mercury vapour), and electrons are
accelerated using a potential. The current is measured as a function of the accelerating voltage applied
to the electrons.

Observations:

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The current increases with voltage, but then drops sharply when V reaches a certain value (4.88 V
here). This indicates the onset of a phenomenon which takes energy from the electrons and prevents
them from reaching the collector. For V>4.88 V, the vapour emits in the UV with a wavelength of
2537 Å.

Explanation:
The accelerated electrons acquire KE from the potential (eV). Suppose the atoms have well defined
and quantised allowed energies (i.e. not continuous). If the energy of the electrons is less than the
energy separation between two energy levels then there can be no energy transfer from the electrons
and the current simply increases as the voltage (and therefore their kinetic energies) increases. On the
other hand, if the kinetic energy of the electrons equals the energy separation between two energy
levels (E1 and E2) then the atom absorbs this energy (KE=E2-E1=4.88 eV) and hence raises its energy
from its ground state (E1) to its first excited state (E2) by inelastic collision with the electron (fig a).

E2 E2
hn E2  E1

E1 E1

a) KE=E2-E1 b)

Later, the atom “decays” back to its ground state by emitting a photon of energy hn=E2-E1=4.88 eV
(fig b), giving rise to the observed spectral line. In (a), the impinging electron has lost all its energy
and hence cannot contribute to current. As the bias voltage is increased further, the KE of the removed
electron increases once again and so current increases. Accelerated electrons removed in the collision
can be re-accelerated to produce other inelastic collisions at 4.88 eV, hence the current drops
periodically when the voltage reaches multiples of 4.88V.

Thermal occupancy of levels in atoms:


Thermal energy causes random motion in a gas (i.e. generates KE of the atoms). This thermal energy
is ~kBT per atom for a monatomic gas, where T is the temperature in degree Kelvin, and kB is
Boltzmann’s constant (this result comes from statistical mechanics). Collisions cause excitations, and
hence some higher energy states will be occupied. Take an atom at a temperature T, and consider the
number (N1) of electrons in an energy state E1 compared to the number (N2) in an excited higher
energy state E2.

E2
N2   E  E1  
exp   2 
N1  k BT 
E1

Occupation of E2 is only likely if kBT is comparable with (E2-E1).

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Example: Take hydrogen at 2000°C. What is the relative occupation of the n = 1 & n = 2 states at
20000C (= 2273K) ?
Answer: k BT 1.38 ´10  23 ´2273 3.14 ´10  20 J 0.196 eV

 1 1
E2  E1  13.6    10.2 eV
 4 1
N2  10.2   23
Hence exp    2.5 ´10
N1  0.196 

- which is tiny !

Practice Question - Section 4.5


Try to answer this question yourself, before checking your work against the model answer provided at
the end of this document.
6. What temperature gives a thermal energy of the order of the ionization energy of a H atom?

4.6 Reduced Mass and Nuclear Motion


It has been found that the calculated values of RH and of the ionisation energy for H are within 0.1% of
the observed experimental values. The reason for the slight discrepancy is that the Bohr model
assumes that the proton is massive and is at rest, whereas in fact mp=1836.2 me, so it is finite. Better
agreement is obtained if is considered that the proton and electron both revolve in circular orbits about
their common centre of mass. This motion of the nucleus can be taken into account by simply
replacing the mass of the electron in Bohr’s equations by the reduced mass, , defined by:
me mN

me  mN
Substituting for the proton mass mN = mp   0.99946 mefor H.

So re-calculating the Rydberg’s constant for hydrogen, using the reduced mass in place of the electron
mass:
e 4 me e 4 1 1 1
RH   R¥ R¥ 0.99946 ´R¥
8c 02 h3 8c 02 h3     (1.00054)
 1  me   1  me 
 mp   mp 
   

where R¥ is the (previous) value of the Rydberg’s constant, where infinite nuclear mass was assumed.

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me e 4 1 1
RH  R¥
8c 0 h 
2 3
m   m 
 1  e   1  e 
 mp   mp 
A practical consequence of this refinement of the theory is that it is possible to detect the shift in

spectral lines of isotopes due their different nuclear masses.
Deuterium: 1p, 1n, 1e l 3 2 6563 A 
Hydrogen: 1p, 1e, l 3 2 6561 A A
- so the two lines are separated by 2Å.

4.7 Bohr Theory for Hydrogen-Like Atoms

• We can extend the Bohr theory to other one electron species, eg He+, Li2+, etc. Such species are
known as hydrogen-like atoms.
• Nucleus charge = Ze (where Z is the atomic number = number of protons in nucleus)
• We can use the Bohr equations but must replace e2 by Ze2 throughout.

• Allowed energy levels : me Z 2e 4  1  RH hcZ 2


En     , n 1, 2, 3...
8 02 h2  n 2  n2
 Energy levels multiplied by Z2 compared to the simple hydrogen atom.

• Angular momentum is quantised


L mevr n n 1,2,3...

• Orbital radii are quantised


 0 h 2  2  a0  2 Orbits radii divided by Z compared to H.
rn   n   n , n 1,2,3....
 4m Ze 2   Z 
 e 
• Electron velocity
velocities multiplied by Z compared to H.
Ze 2  1 
vn   
2 0 h  n 
• Transition between two levels ni and nf:
 1 1 
n ( ni , nf ) c RH Z 2  2  2 
 nf ni 
Note: The reduced mass correction becomes even smaller as the nuclei become more massive than just
the single proton of H.

Practice Question - Section 4.7


Try to answer this question yourself, before checking your work against the model answer provided at
the end of this document.
7. Consider transitions from (a higher) energy level ni to (a lower) energy level nf in singly-ionized
helium (He+). Which values of nf are capable of giving rise to spectral lines that fall into the visible
region (400-700 nm)?

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4.8 Limitations of the Bohr Model


• Model is successful at predicting the energy levels of atomic hydrogen.
• It is successful in accounting for all the spectral lines for hydrogen.
• It introduces the idea of quantisation.
• The Bohr frequency rule can be applied to all quantum systems.
But
• It is a hybrid theory between classical and quantum physics.
• The postulate that the orbits can only be circular is arbitrary.
• It cannot predict the intensities of spectral lines.
• Quantisation of angular momentum is introduced in an ad hoc way.
• It cannot be generalised to atoms with more than one electron.

4.9 Bohr’s Correspondence Principle (1923)

“Quantum theory results must tend asymptotically to those obtained


from classical mechanics in the limit of large quantum numbers”.

The quantum world is sub-microscopic, and it involves small quantum numbers.


Macroscopic scales of radius say ~1 cm need rn=a0n2=1´10-2 ®n~13736.

En  En  1  1 1 
n   RH c  2 
h n  n  1 2 
 n 2  ( n  1)2   2n  1 
n RH c  2  RH c 
2 

 n 2 ( n 2  1  2n ) 
 n  n  1   
2n 2cRH
n ~ cRH 4
 ®0
n n3
n® ¥
Results in vanishingly small steps  continuous spectra
 Quantum mechanics converges towards classical mechanics for large quantum numbers.
 Correspondence principle: valid for all other quantum mechanical systems.

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Bohr model for Hydrogen-like atoms - summary:

• Angular momentum L is quantised L n n 1, 2, 3..

• Electron on stable orbits with quantised radii a 


rn  0  n 2 , n 1,2,3.... 
 Z  a0 0.53 A

• Velocity in orbit is quantised 1


vn  n 1, 2, 3...
n

RH hcZ 2
• Allowed energies are quantised E n  , n 1, 2, 3...
n2

Ei  E f
• Bohr Frequency rule: transition n
h

 1 1 
n (ni , n f ) cRH Z 2  2  2 
• Transition between two levels ni and nf n 
 f ni 

where Z is the atomic number = number of protons in nucleus


 me  1  1 1 
RH R¥  1   RH Z 2  2  2 
 m  l n 
nucleus  f ni 

Answer to Practice Question - Section 4.3

1. 3rd excited state  n = 4. rn = a0 n2  r4 = 0.53 x 42 = 8.5 Å

Answers to Practice Questions - Section 4.4

2. En = - 13.6 / n2 eV  E10 = - 13.6 / 102 = - 0.136 eV & E1 = - 13.6 eV


 E = 13.6 - 0.136 = 13.46 eV = 2.154 x 10-18 J
E = h c / λ  λ = h c / E = 6.63 x 10-34 x 3 x 108 / 2.154 x 10-18 = 923 Å

3. En = - 13.6 / n2 eV  E2 = - 13.6 / 22 = - 3.4 eV & E∞ = 0 eV


 E = 3.4 eV = 5.44 x 10-19 J
E = h c / λ  λ = h c / E = 6.63 x 10-34 x 3 x 108 / 5.44 x 10-19 = 366 nm

4. En = - 13.6 / n2 eV  E3 = - 13.6 / 32 = - 1.511 eV


E = h c / λ
 EA = 6.63 x 10-34 x 3 x 108 / 1875.1 x 10-9 J = 0.663 eV
& EB = 6.63 x 10-34 x 3 x 108 / 1281.8 x 10-9 J = 0.970 eV
 EA = - 1.511 + 0.663 = - 0.848 eV & EB = - 1.511 + 0.970 = - 0.541 eV
En = - 13.6 / n2  n = (- 13.6 / En)  A = (- 13.6 / - 0.848) = 4 & B = (- 13.6 / - 0.541) = 5

5. En = - 13.6 / n2 eV  E7 = - 13.6 / 72 = - 0.278 eV

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lOMoARcPSD|13376894

Longest wavelength of emission corresponds to smallest photon energy & hence the smallest
transition, which is therefore to the n = 6 level.
E6 = - 13.6 / 62 = - 0.378 eV  E = 0.378 - 0.278 = 0.100 eV = 1.60 x 10-20 J
E = h c / λ  λ = h c / E = 6.63 x 10-34 x 3 x 108 / 1.6 x 10-20 = 12.4 µm
Ionisation takes the electron to E∞ = 0 eV
 E = 0.278 eV = 4.45 x 10-20 J  λ = 6.63 x 10-34 x 3 x 108 / 4.45 x 10-20 = 4.5 µm

Answer to Practice Question - Section 4.5

6. Ionisation energy of H atom is 13.6 eV = 2.18 x 10-18 J


Thermal energy  kB T  T  2.18 x 10-18 / 1.38 x 10-23  1.6 x 105 K

Answer to Practice Question - Section 4.7

7. Transition between two levels ni and nf:


 1 1 
n (ni , n f ) c RH Z 2  2  2 
 n f ni 
 
1
  1 1   ni2 n 2f ni2 n 2f
 l (n , n )  R Z 2 
 H  2  2    
RH Z 2  ni2  n 2f   
i f
  n f ni   4.387 ´107 ni2  n 2f

Transitions to nf = 1:
Longest wavelength will be from ni = 2, which gives λ = 30.4 nm, which is too short to be visible.

Transitions to nf = 2:
Longest wavelength will be from ni = 3, which gives λ = 164 nm, which is too short to be visible.

Transitions to nf = 3:
Longest wavelength will be from ni = 4, which gives λ = 469 nm, which is visible.

Transitions to nf = 4:
Longest wavelength will be from ni = 5, which gives λ = 1013 nm, which is too long to be visible.
Shortest wavelength will be from ni = ∞, which gives λ = 365 nm, which is too short to be visible.
Trying something in between, say ni = 7, gives λ = 542 nm, which is visible.

Transitions to nf = 5:
Longest wavelength will be from ni = 6, which gives λ = 1865 nm, which is too long to be visible.
Shortest wavelength will be from ni = ∞, which gives λ = 570 nm, which is visible.

Transitions to nf = 6:
Longest wavelength will be from ni = 7, which gives λ = 3093 nm, which is too long to be visible.
Shortest wavelength will be from ni = ∞, which gives λ = 821 nm, which is also too long to be
visible.

Following this trend, transitions to nf > 6 will all have wavelengths that are too long to be visible,
so only nf = 3, 4 & 5 give any visible lines.

There are more practice problems (together with just their final answers) for the whole of this
section: they can be found in a separate document at the end of this distance learning package.

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