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PHYSICS OF THE ATOM

(PH351)
LECTURE #4
4.0 ATOMIC SPECTRAL
Content:
4.1. Emission and Absorption spectrum (spectral lines)
4.2. The emission spectrum of hydrogen atom
4.3. The visible spectrum of hydrogen atom: Balmer’s formula
4.4. Rydberg formula
4.5. The ultraviolet (UV) and infrared (IR) series for hydrogen
4.6. Prediction of hydrogen spectrum series by Bohr’s model
4.7. Solar spectrum - Fraunhofer lines 2
Emission and Absorption Spectrum (spectral lines)
 Atoms of each element are capable of emitting or absorption light.
 In emission an atom loses energy which is carried away by the light that it emits. The pattern of emitted
wavelengths is known as the emission spectrum of the atoms.

• Often the emission spectrum consists of a set of characteristic emission lines and the spectrum is then often
referred to as the emission line spectrum (emission spectral lines).

 In absorption an atom gains energy from the incoming light which it absorbs. The pattern of absorbed
wavelengths is known as the absorption spectrum of the atoms.

How spectral emission occur?

 Emission occurs when an electron transitions, or jumps, from a higher energy state to a lower energy state,
with the energy difference carried away by an emitted photon.
Energy of Photon = - [ Energy of Final State - Energy of Initial State ]

 The emitted photon typically covers a range of wavelengths and, when appropriately dispersed, so that
different wavelengths travel in different directions, it reveals what is known as the emission spectrum of
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the substance.
Spectral Emission
(a) An emission process is one in which
the electron makes a transition to a lower
energy level, with the energy difference
carried away by an emitted photon.

(b) An absorption process is one in which

the electron absorbs sufficient energy from
an incident photon to move to a higher
energy level.
Figure. Emission and absorption transitions in atomic hydrogen,
shown on the energy diagram.

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 The emission spectrum of atomic hydrogen
 The understanding of atomic spectra must begin with simplest atom of all, the hydrogen. Because, the
interpretation of spectra from multi-electron atoms is complicated, even by today’s standards.
 To observe the spectrum of atomic hydrogen requires the hydrogen molecules to be broken into individual
atoms, a process known as dissociation.

• Fortunately the conditions existing within a spectral lamp (discharge hydrogen lamp), cause dissociation
of many of the H2 molecules and so the atomic hydrogen spectrum is quite easy to produce.

o When the atoms of a gas are excited (for example by an electric discharge tube), they emit light. After passing
through a prism or gratings , and projected in a screen, the light appears in the form of lines. 
 Hydrogen spectrum consists of a set characteristic lines in the visible part of the electromagnetic spectrum, one
set in the ultraviolet region and several sets in the infrared region.

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The visible spectrum of atomic hydrogen: Balmer’s formula
 Although physicists were aware of atomic emissions of hydrogen before 1885, but they lacked a tool to
accurately predict where the spectral lines should appear.
 Explaining the nature of the hydrogen spectrum was a considerable problem in physics. Nobody could
predict the wavelengths of the hydrogen lines.
• Until 1885 when a Swiss mathematics teacher, (Johann Jakob Balmer), by trial and error found an
interesting mathematical formula which describes the wavelengths of the known visible lines in the spectrum
of atomic hydrogen.
Where
λ = is the wavelength.
The Balmer formula is given by; B = is a constant 364.50682 nm.
m = integer equal to 2
n = is an integer such that n > m.
• Balmer noticed that a single number had a relation to every line in the hydrogen spectrum that was in the visible
and light region. That number was 364.50682 nm. (Balmer constant)
 n2 
  364.56  2  ( Balmer ' s formula ) 1
n 4
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Balmer Series
 The expression has become known as Balmer formula and the spectral lines whose wavelengths fit this
formula become known as the Balmer series.

 The Balmer equation predicts the four visible emission lines of hydrogen (Balmer series) with high accuracy.

 The observed lines have wavelengths 656.21 nm (red), 486.07 (blue/green), 434.01 nm (blue/violet) and
410.12 nm (violet).

• Balmer lines are historically referred to

as "H-alpha", "H-beta", "H-gamma" and
 n2 
so on, where H is the element hydrogen.   364.56  2  ( Balmer ' s formula) 1
n 4
 Four of the Balmer lines are in the
technically "visible" part of the
spectrum, with wavelengths longer
than 400 nm and shorter than 700 nm.
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Rydberg formula 
 The Rydberg formula is used in atomic physics to describe the wavelengths of spectral lines of
many chemical elements. It was formulated by the Swedish physicist Johannes Rydberg in1888.
• Rydberg worked on a formula describing the relation between the wavelengths in spectral lines of
alkali metals.
 Rydberg managed to find a formula (rewrote Balmer's formula in terms of reciprocal of wavelength) to
match the known Balmer series emission lines, and also predicted those not yet discovered.
1  1 1 
The Rydberg formula is given by;  RH  2  2 
  nf ni 


 Where λ is the wavelength of electromagnetism radiation emitted in vacuum, RH is the Rydberg constant
approximately 1.097 x 107 m-1.

• Where ni and nf are integers, 1, 2, 3, 4, 5 … up to infinity, with nf >ni. For the hydrogen atom, nf = 2
corresponds to the Balmer series. There are other series in the hydrogen atom that have been measured.
• The Rydberg constant can be written in terms of Balmer constant as RH = 4/B
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Limitation of Rydberg Formula
 It's important to notice that this formula can be directly applied only to hydrogen-like, also called
hydrogenic atoms of chemical elements.

• i.e. atoms with only one electron being affected by an effective nuclear charge (which is easily estimated).
Examples would include He+, Li2+, Be3+ etc., where no other electrons exist in the atom.

• The formula above can be extended for use with any hydrogen-like chemical elements with modification

1  12 1 
 RH Z  2  2  Where Z2 is the atomic number
  nf n 
 i 

 For other spectral transitions in multi-electron atoms, the Rydberg formula generally
provides incorrect results, since the magnitude of the screening of inner electrons for outer-electron
transitions is variable and not possible to compensate for in the simple manner.
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The ultraviolet (UV) and infrared (IR) series of spectral lines for hydrogen
 There are other series of atomic hydrogen spectral lines which known today but which were not known to Balmer.

4.5.1. Lyman Series

 One series of lines in the far ultraviolet (UV), the Lyman Series. The series is named after its discoverer, Harvard
physicist Theodore Lyman, who discovered the spectral lines from 1906–1914. All the wavelengths in the Lyman
series are in the ultraviolet band. (They cannot be seen by naked eyes. They can be photographed)
 In atomic physics, the Lyman series is a hydrogen spectral series of transitions and resulting ultraviolet
emission lines of the hydrogen atom as an electron goes from ni ≥ 2 to nf= 1

• The first line in the spectrum of the Lyman series was discovered in 1906, when Theodore
Lyman was studying the ultraviolet spectrum of electrically excited hydrogen gas.

• The member corresponding to n2 = ∞ is called limiting member,

1 1
• limiting member, has shortest wavelength given by;   91.2 nm
 RH
1 1 1
 1.097 107  2  2  ni  2, 3, 4, 5, 6.....
  1 ni 
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Paschen series (nf = 3, ni ≥ 4 ) Brackett series (nf = 4, ni ≥ 5 )
• Named after the German physicist Friedrich Named after the American physicist Frederick Summer
Paschen who first observed them in 1908. Brackett who first observed the spectral lines in 1922.
The Paschen lines all lie in the infrared band.
1 7 1 1
 1.097 10  2  2  ni  5, 6.....
1 7 1 1 
 1.097 10  2  2  ni  4, 5, 6.....  4 ni 
  3 ni 

 The vertical arrows in Fig above. represent the transitions or

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jumps that correspond to the various observed spectral lines.
Pfund series (nf = 5, ni ≥ 6 ) Humphreys series (nf = 6, ni ≥ 7 )
• Experimentally discovered in 1924 • Discovered in 1953 by American physicist
by August Herman Pfund Curtis J. Humphreys

1 7 1 1
1 1 1  1.097 10  2  2  ni  7, 6.....
 1.097 107  2  2  ni  6, 7, 8.....   6 ni 
  5 ni 

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Further (nf > 6)
 Further series are unnamed, but follow the same pattern as dictated by the Rydberg equation. Series are
increasingly spread out and occur in increasing wavelengths.

 The lines are also increasingly faint, corresponding to increasingly rare atomic events.

 The seventh series of atomic hydrogen was first demonstrated experimentally at infrared wavelengths in
1972 by John Strong and Peter Hansen at the University of Massachusetts Amherst.

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Prediction of hydrogen spectrum series by Bohr’s model
 It is important now to test whether Bohr’s model is able to predict the wavelengths of the hydrogen spectrum.

 According to Bohr Theory, the electron in a hydrogen atom have definite energy levels. At room
temperature, nearly all hydrogen atoms will be in the ground state.
 At higher temperatures, or during an electric discharge when there are many collisions between free electrons
and atoms, many atoms can be in excited states.

• Once in an excited state, an atom's electron can jump down to a lower state, and give off a photon in the
process. This is, according to the Bohr model, the origin of the emission spectra of excited gases.

mZ 2 e 4  1 
En   2 2  2  13
8 o h  n 

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Prediction of hydrogen spectrum by Bohr’s model
We rearranging the equation, we get

Where, R is the Rydberg constant

Then, we get Which is value is 1.097 x 107 m-1

 For example, an electron jumping from (ni =2 to nf = 1) it will give the first member of Lyman series, from
(ni =3 to nf = 2) it will give the first member of Balmer series, and from (ni =4 to nf = 3) it will give the first
member of Paschen series etc.

“By appropriate choices of ni and nf in the Bohr’s model, it is possible to show all lines in the hydrogen
spectrum (from Balmer to Humphreys series)”.

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Solar spectrum - Fraunhofer lines
 The spectrum of light emitted by the sun is called solar spectrum, which is a bright colored continuous
spectrum crossed by a larger number of dark lines.
• The line was first observed by English chemist William Wollaston in 1802.
 Later in 1817 it was then studied by German physicist Joseph Von Fraunhofer (sometimes these spectral lines
of the sun called Fraunhofer lines), who located hundreds of these lines and labeled eight of the most
prominent lines as A, B, C, D, E, F, G and H as shown in the diagram.

 The presence of dark lines are due to the absorption of light by various elements present in the
atmosphere.
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Lecture #4 Questions
1. The ionization potential of an atom is 4.2 eV. Calculate the series limit in its absorption spectrum.
2. The second member of Lyman series in hydrogen spectrum has a wavelength of 5400 Ao. calculate the
wavelength of the first member (Given RH= 1.097x10-7m)
3. Why we obtain several lines in emission spectrum of hydrogen atom while it has only one electron?
4. The series limit wavelength of Balmer series in hydrogen spectrum is experimentally found to be 3646 Ao.
Find the wavelength of the first member of the series.
5. The energy levels of an atom are shown in Fig. 1.1. Which one of these transitions results in the emission of
a photon of wavelength 275 nm? Show by calculation

6. Calculate the wavelength of the first two lines of the Paschen series.
7. Can a hydrogen atom absorb a photon whose energy exceeds its binding energy (13.6 eV)? Explain why not
if the answer is no and how if the answer is yes.
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8. An electron in hydrogen atom makes a transition from initial energy, Ei to final energy, Ef state thereby
emitting a 489 nm photon. If the excitation energy of the final state is 10.19 eV. Calculate the binding energy
of the initial state and indicate the value of the subscript “i” for this state.
9. An electron undergoes successive transitions in a hydrogen atom. Initially the electron is in the state n a = 6.
In the first transition, to an intermediate state nb a photon of energy 1.13 eV is emitted. After the second
transition, the electron is in the ground state nc =1.
(a) Determine the quantum number, nb for the intermediate state
(b) Determine the energy of the photon emitted in the second transition
(c) Show these two transitions on an energy level diagram for hydrogen.
10. An atom absorbs a photon having a wavelength of 375 nm and immediately emits another photon having a
wavelength of 580 nm. What was the net energy absorbed by the atombm in2this process?
11. Show that the Balmer series formula can be written in the form m  m2  n 2 where b is a constant, n = 2 and

m = 3, 4, 5……This is the form originally proposed by Balmer.

(a) Express b in terms of the Rydberg constant RH.
(b) What is the numerical value of constant b?

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12.The wavelength of the first line Lyman series for hydrogen is identical to that of the second line of Balmer
series for hydrogen like ion X. Calculate the energies of the first four level of X. Also find its ionization
potential. Given ground state binding energy of hydrogen atom = 13.6 eV.
 
13.Can hydrogen atom absorb a photon having energy more than 13.6 eV?
 
14.In atomic spectrum, only certain discrete lines are found why?
 
15.Is it possible to get the absorption spectrum corresponding to all the series in emission spectrum? Why?
 
16.The wavelength of the sodium D1 line is 5890 Ao. Find the difference in energy levels involved in the
emission of this line.
 
17.During the transition to the ground state, what is the longest wavelength of light that can be emitted by
hydrogen.

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END OF
LECTURE #4

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