Electromagnetic Spectrum

Simple Experimental set up of a Discharge emission

Simple Experimental Prism set up Sodium D1 and D2 Lines
Simple Experimental set up with Diffraction Grating
 White light Grating spectra

White Light
Simple Experimental set up of a Arc Discharge emission
The difference between absorption and emission spectra are that

Absorption lines are where light has been absorbed by the atom thus you see a dip in
the spectrum

whereas
Emission spectra have spikes in the spectra due to atoms releasing photons at those
wavelengths
 Optical Spectrometer and emission spectra
where d is
“line spacing
Note that on the
there is a diffraction
high voltage grating”
rather than
a couple of
volts as in
the Frank-
Hertz
experiment gasses in tubes are typically
quite dilute, discrete spectra
If highly excitated due to high tension, there are many different transitions
downwards, so typically more emission lines than absorption lines
 Spectroscopy can be done very precisely, in fact so precisely that isotopes
of hydrogen, were discovered that way, Deuterium as early as 1932, later
on also Tritium)
 Much depends on the quality of the grating …spectroscopic
measurements can be very precise, one can distinguish between 12
isotopes of hydrogen
Absorption spectra, light of certain wavelengths is taken out of the “quasi
black-body spectrum” of the sun, the glass prism provides a limited dispersion so
that the emission lines from the excited atoms in the sun are not readily visible

It is typically only transition from the ground state to higher states

that are missing in the otherwise continuous spectrum from the
13
sun, so it is only a few
 Bohr's Model of the Hydrogen Atom
Basic Principles of Spectroscopy
o The most important sources of information about the
electronic structure and composition of atoms are spectra
in the visible, infrared, ultraviolet, x-ray, microwave and
radio frequency ranges.
o Optical spectra are further categorised as line, band and
continuous spectra. Continuous spectra are emitted by
radiant solids or high-density gases.
o Band spectra consist of groups of large numbers of spectral
lines which are very close to one another. They are
generally associated with molecules.
o Line spectra, on the other hand, are typical of atoms. They
consist of single lines, which can be ordered in
characteristic series.
o Optical spectra can be observed either by emission or by
absorption.
o The emission mode requires that the substance to be
examined be made to emit light; this can be achieved by
transferring energy to the atoms by means of light, electron
collisions, x-ray excitation or some other process.
o If a substance re-emits the light it has absorbed, the process is
called resonance fluorescence.
 Units of Spectra
• Spectra are traditionally measured in several different units,
due to the features of the apparatus or for practical reasons:
• - In wavelength units.
• - Specifying the frequency is more general, since it is not
dependent on the medium
• - A frequently cited quantity is the wavenumber
𝜈 1 1
𝜈ҧ = = =
𝑐 𝜆𝑣𝑎𝑐 𝑛𝜆𝑎𝑖𝑟
The wavenumber is, like the frequency, a quantity proportional
to the energy; conversion may be made according to the
equation
𝐸 = 𝜈ℎ𝑐ҧ
• - Finally, the unit electron volt (eV) is often used as a measure
of the energy.
Frequently used conversion factors
 The Optical Spectrum of the Hydrogen Atom
• Kirchhoff and Bunsen, the founders of
spectroscopic analysis, were the first to
discover in the mid-19th century that
each element possesses its own
characteristic spectrum.
• Hydrogen is the lightest element, and the
hydrogen atom is the simplest atom,
consisting of a proton and an electron.
• The spectra of the hydrogen atom have
played an important role again and again
over the last 90 years in the development
of our understanding of the laws of
atomic structure and of the structure of
matter.
 The Optical Spectrum of the Hydrogen Atom
• The emission spectrum of atomic hydrogen
shows three characteristic lines in the visible
region at 6563, 4861, and 4340 Å (𝐻𝛼,𝛽,𝛾 ).
• The most intense of these lines was discovered
in 1853 by Angstrom; it is now called the 𝐻𝛼
line.
• In the near ultraviolet region, these three lines
are followed by a whole series of further lines,
which fall closer and closer together in a regular
way as they approach a short-wavelength limit
(𝐻∞ )
 The Optical Spectrum of the Hydrogen Atom

• Balmer found in 1885 that the wavelengths of these lines

could be extremely well reproduced by a relation of the form
𝑛12
𝜆= 2 𝐺
𝑛1 − 4
Here n1 =3,4 .. And G is empirical constant.
• Today, we write the Balmer formula somewhat differently. For
the wavenumbers of the lines we write
1 1 1
𝜈ҧ = = RH 2 − , n>2
𝜆 2 n2
• The quantity R H = 4/𝐺 is called the Rydberg constant and
has the numerical value R H = 109677.5810 cm-1
𝑅𝐻
• The series limit is found for n → ∞ to be 𝜈ҧ =
4
The Optical Spectrum of the Hydrogen Atom
• For the further investigation of the hydrogen spectrum, astrophysical
observations have played an important role. In the spectra of stars,
photographically recorded as early as 1881 by Huggins, a large number of
lines from the hydrogen spectrum are seen.
• Using modern radio-astronomical techniques, transitions between states
with extremely large n-values have been found; levels with n between 90
and 350 could be identified.
• The reason that many lines were discovered first in astrophysical
observations and not by experiments on the earth is connected with the
difficulty of preparing pure atomic hydrogen in the laboratory.
• Gas discharges, in which H2 gas is decomposed into atomic hydrogen and
excited to fluorescence, always contain fluorescing hydrogen molecules as
well, whose spectrum overlaps the atomic-hydrogen spectrum.
• Above the series limit we observe the so-called series-limit continuum, a
region in which the spectrum shows no more lines, but is, instead,
continuous.
 The Optical Spectrum of the Hydrogen Atom
The whole spectrum of the H atom is represented by equations of the form
1 1 1
νത = = R H ′2 − 2 with n' <n being integers .
λ n n
This relation was formulated first by Rydberg in 1889. He found, "to his great
joy", that the Balmer formula is a special case of the Rydberg formula
The Optical Spectrum of the Hydrogen Atom
The wavelengths of some lines of the various spectral series in
hydrogen. The series with n' = 5 was observed in 1924 by
Pfund; it begins with a line of λ = 74000 Å, but is not shown in
the table
 Thomson’s Atomic Model

 Thomson’s “plum-pudding” model of the atom had the positive charges

spread uniformly throughout a sphere the size of the atom, with
electrons embedded in the uniform background.

 In Thomson’s view, when the atom was heated, the electrons could
vibrate about their equilibrium positions, thus producing
electromagnetic radiation.

That is the dough or pudding in the plum pudding? the plums/raisins are the electrons 24
 Rutherford’s Atomic Model
 Rutherford proposed that an atom has a positively charged core
(nucleus) surrounded by the negative electrons.

Something three–dimensional where there

is a particle nucleus and particle electrons in
certain orbits, not correct

There is no positively charged dough or pudding in the plum pudding/raisin cake, only 25
raisins, empty space, and a core
 4.3: The classical/solar system Atomic Model
is doomed
Let’s consider atoms as a quasi sun/planet model (only one planet so that it is
just a two body problem.
The force balance of circular orbits for an electron “going around” a stationary
nucleolus

For the centripetal force

in a circular orbit

where v is the tangential velocity of the electron.

Circular motion is accelerated, accelerated charges need to radiate energy
off according to Maxwell, loosing kinetic energy

26
Other weaknesses:
(1) gravity in the solar system is attractive, if there is
more than one electron in an atom, they will repel
each other.
(2) most importantly: if two solar system atom models
were to “collide”, they would form a “molecule model”,
but when that “molecule model” is broken up, there is
no physics that would ensure that the two original
“solar system atom models” would be obtained again.

27
 Bohr’s Postulates
• Bohr assumed that the electrons move around the nucleus in
circular orbits of radius r with velocity v, much as the planets move
around the sun in the Solar System.
• A dynamic equilibrium between the centrifugal force and the
Coulomb attraction of the electrons to the nucleus is assumed to
exist. Thus, for the hydrogen atom, one has
𝑒2 2
= 𝑚 0 𝑟𝜔
4𝜋𝜀0 𝑟 2
• The corresponding energy is the sum of the kinetic and the
potential energies of the electrons:
𝐸 = 𝐸𝑘𝑖𝑛 + 𝐸𝑝𝑜𝑡
• The potential energy is defined as the work which one obtains on
allowing the electron to approach the nucleus under the influence
of the Coulomb force from infinity to a distance r.
BOHR ATOM MODEL STRATEGY
• Since the work is defined as the product of force and distance, and the Coulomb
force changes continuously with the distance from the nucleus, we must integrate
the contributions to the work along a differential path dr, this gives
𝑟
𝑒2 𝑒2
𝐸𝑝𝑜𝑡 = න ′2
𝑑𝑟′ = −
∞ 4𝜋𝜀0 𝑟 4𝜋𝜀0 𝑟
• The total energy is thus found to be
2
1 𝑒
𝐸 = 𝑚0 𝑟 2 𝜔 2 −
2 4𝜋𝜀0 𝑟
𝑒2 𝑒 4 𝑚0 𝜔2 1/3
𝐸=− =−
2 ∙ 4𝜋𝜀0 𝑟 2 4𝜋𝜀0 2/3
• Classically, orbits of arbitrary radius and thus a continuous series of energy values
for the electron in the field of the nucleus should be allowed. But on identifying
the energy levels which are implied by the spectral series with the values of the
electron's energy, one is forced to assume that only discrete energy values are
possible.
• Furthermore, electrons moving in circular orbits are accelerated charges, and as
such, they should radiate electromagnetic waves with frequencies equal to their
orbital frequencies, 𝜈 = 𝜔/2𝜋. They would thus lose energy continuously, i.e.
their orbits are unstable and they would spiral into the nucleus. Their orbital
frequencies would change continuously during this process. Therefore, the
radiation emitted would include a continuous range of frequencies.
• In order to avoid this discrepancy with the laws of classical physics, Bohr
formulated three postulates which describe the deviations from classical
behavior for the electrons in an atom. These postulates proved to be an
extremely important step towards quantum mechanics. They are:
1. The classical equations of motion are valid for electrons in atoms.
However, only certain discrete orbits with the energies En are allowed.
These are the energy levels of the atom.
2. The motion of the electrons in these quantised orbits is radiationless. An
electron can be transferred from an orbit with lower (negative) binding
energy En (i.e. larger r) to an orbit with higher (negative) binding energy
En, (smaller r), emitting radiation in the process. The frequency of the
emitted radiation is given by
𝑅ℎ𝑐 𝑅ℎ𝑐
𝐸𝑛 − 𝐸𝑛′ = ℎ𝜈, where 𝐸𝑛 = − 2 and 𝐸𝑛′ = − ′2
𝑛 𝑛
Light absorption is the reverse process.
3. Finally, for the calculation of the Rydberg constant R in from atomic
quantities, Bohr used the comparison of the orbital frequencies of the
electrons with the frequency of the emitted or absorbed radiation.
Correspondence Principle
Bohr's decisive idea was then to postulate that with increasing orbital radius
r, the laws of quantum atomic physics become identical with those of
classical physics. The application of this "Correspondence Principle" to the
hydrogen atom allows the determination of the discrete stable orbits.

We consider the emission of light according to the first two postulates for a
transition between neighbouring orbits, i.e. for (n-n') = 1, and for large n.
We have for the frequency v, with n-n' = τ
1 1 1 1
𝜈 = 𝑅𝑐 ′2 − 2 = 𝑅𝑐 −
n n (n − 𝜏)2 n2
1 1 2𝜏
= 𝑅𝑐 2 − 1 = 𝑅𝑐
n (1 − 𝜏 )2 𝑛3
n
3
With 𝜏 = 1, 𝜈 = 2𝑅𝑐/𝑛
1 1
4 2 3 2 3
𝑅ℎ𝑐 𝑒 𝑚0 𝜔 1 1 4
2𝜋2𝑅𝑐
𝐸=− 2 =− 2 = 2 𝑒 𝑚0
𝑛 2 𝑛3
2 4𝜋𝜀0 3 4𝜋𝜀0 3
4
𝑚0 𝑒
𝑅=
8𝜀02 ℎ3 𝑐
 Bohr’s Correspondence Principle specific for orbits
of hydrogen atom
• The frequency of the radiation emitted fclassical is equal to the orbital frequency forb
of the electron around the nucleus.

• The frequency of the transition from n + 1 to n is

• For very large n only,

Substitute for E0:

From this idea he actually figured angular momentum needs to be 34

quantized in units of for the mathematics to work out
• In addition, we may calculate the orbital angular
momentum 𝑙 = 𝑟 × 𝑝 of an electron having velocity 𝑣𝑛 and
orbital frequency 𝜔𝑛 in the orbit with radius 𝑟𝑛 .
2𝑅𝑐 4𝜋𝑅𝑐
• 𝜈= ⟹ 𝜔𝑛 = 2𝜋𝜈 = 3
𝑛3 𝑛
𝑛2 ℏ2 4𝜋𝜀0 𝑚0 𝑒 4
• Since 𝑟𝑛 = 2 and 𝑅 = 2 3
𝑒 𝑚0 8𝜀0 ℎ 𝑐
2
𝑛2 ℏ2 4𝜋𝜀0 4𝜋𝑐 𝑚0 𝑒 4
|𝑙| = 𝑟 × 𝑝 = 𝑚0 𝑟𝑛2 𝜔 = 𝑚0
𝑒 2 𝑚0 𝑛3 8𝜀02 ℎ3 𝑐
|𝑙| = 𝑛ℏ with n = 1,2,3..

This quantisation rule is often (but incorrectly) taken to be

one of Bohr's postulates
BOHR’S POSTULATES (Presented Now)
Energy Calculation
 Bohr model for hydrogen-like systems
• For H-like systems e.g., He+, Li2+, Be3+, .. And so on
𝑍𝑒 2 2
= 𝑚 0 𝑟𝜔
4𝜋𝜀0 𝑟 2
𝑛2 ℏ2 4𝜋𝜀0
Radius of nth orbit: 𝑟𝑛 =
𝑍𝑒 2 𝑚0
1 𝑍 2 𝑒 4 𝑚0
Angular frequency: 𝜔𝑛 =
4𝜋𝜀0 2 𝑛3 ℏ3
1 𝑍𝑒 2
Total Energy: 𝐸𝑛 = 𝑚0 𝑣𝑛2 −
2 2∙4𝜋𝜀0 𝑟𝑛
2 4
𝑍 𝑒 𝑚0 1
𝐸𝑛 = − 2 2 2 ∙ 𝑛2
32𝜋 𝜀0 ℏ
For Hydrogen atom’s first orbit (Z = n = 1)
E1 = -13.59 eV
For arbitrary Z
𝑍2
𝐸𝑛 = −13.59 2 eV
𝑛
Transitions in Hydrogen
Hydrogen Spectral Series from the Bohr Model
Hydrogen Spectral Series from the Bohr Model
 The Optical Spectrum of the Hydrogen Atom
The whole spectrum of the H atom is represented by equations of the form
1 1 1
νത = = R H ′2 − 2 with n' <n being integers .
λ n n
This relation was formulated first by Rydberg in 1889. He found, "to his great
joy", that the Balmer formula is a special case of the Rydberg formula
 Motion of the nucleus
• The spectroscopically measured quantity 𝑅𝐻 does not agree exactly with
the theoretical quantity 𝑅∞ . The difference is about 60 cm-1 .
• The reason for this is the motion of the nucleus during the revolution of
the electron, which was neglected in the above model calculation.
• This calculation was made on the basis of an infinitely massive nucleus; we
must now take the finite mass of the nucleus into account.
• In mechanics it can be shown that the motion of two particles, of masses
m1 and m2 and at distance r from one another, takes place around the
common centre of gravity. If the centre of gravity is at rest, the total
energy of both particles is that of a fictitious particle which orbits about
the centre of gravity at a distance r and has the mass
𝑚1 𝑚2
𝜇=
𝑚1 + 𝑚2
referred to as the reduced mass.
• The electron and hydrogen nucleus actually revolved about their mutual
center of mass.

• The electron mass is replaced by its reduced mass.

• The Rydberg constant for infinite nuclear mass is replaced by RH for

hydrogen, RD for deuterium, RT for tritium .

See also earlier slide where we

used α instead

All three hydrogen isotopes have a slightly different R values in precision

experiments, a way to detect these isotopes in the sun by their 46
“signature” on earth
• In all the calculations described in the previous slide we must therefore
replace the mass of the orbiting electron m0, by 𝜇 and obtain, in
agreement with experiment,
1
𝑅 = 𝑅∞ 𝑚
1+ 0
𝑀
• Here m0=m1, the mass of the orbiting electron, and M=m2, the mass of the
nucleus.
• Due to the motion of the nucleus, different isotopes of the same element
have slightly different spectral lines.
• This so-called isotope displacement led to the discovery of heavy
hydrogen with the mass number A=2 (deuterium).
 1 −1
𝑅𝐻 = 𝑅∞ ∙ 𝑚 = 109677.584 cm
1+ 0
𝑀𝐻
1 −1
𝑅𝐷 = 𝑅∞ ∙ 𝑚0 = 109707.419 cm
1+
𝑀𝐷

The difference in wavelengths Δ𝜆 for corresponding lines in the

spectra of light and heavy hydrogen is:
𝜆𝐷 𝑅𝐻
Δ𝜆 = 𝜆𝐻 − 𝜆𝐷 = 𝜆𝐻 1 − = 𝜆𝐻 1 −
𝜆𝐻 𝑅𝐷

Comparison of the wavelengths of corresponding spectral lines in

hydrogen and deuterium. The lines belong to the Lyman series
 Bohr model for hydrogen-like systems
• For H-like systems e.g., He+, Li2+, Be3+, .. And so on
𝑍𝑒 2 2
= 𝑚 0 𝑟𝜔
4𝜋𝜀0 𝑟 2
𝑛2 ℏ2 4𝜋𝜀0
Radius of nth orbit: 𝑟𝑛 =
𝑍𝑒 2 𝑚0
1 𝑍 2 𝑒 4 𝑚0
Angular frequency: 𝜔𝑛 =
4𝜋𝜀0 2 𝑛3 ℏ3
1 𝑍𝑒 2
Total Energy: 𝐸𝑛 = 𝑚0 𝑣𝑛2 −
2 2∙4𝜋𝜀0 𝑟𝑛
2 4
𝑍 𝑒 𝑚0 1
𝐸𝑛 = − 2 2 2 ∙ 𝑛2
32𝜋 𝜀0 ℏ
For Hydrogen atom’s first orbit (Z = n = 1)
E1 = -13.59 eV
For arbitrary Z
𝑍2
𝐸𝑛 = −13.59 2 eV
𝑛
 Spectra of Hydrogen-like Atoms
• According to Bohr, the spectra of all atoms or ions with only
one electron (one-electron systems) should be the same
except for the factor Z2 and the Rydberg number.
• The spectrum of hydrogen should thus explain those of the
ions He+, Li2+, Be3+ or any other ions which have only one
electron.
• This has been completely verified experimentally.
• For He+, astronomers found
𝟏 𝟏
• the Fowler series ഥ
𝝂𝑭 = 𝟒𝑹𝐇𝐞 −
𝟑𝟐 𝒏𝟐
𝟏 𝟏
• the Pickering Series ഥ
𝝂𝑷 = 𝟒𝑹𝐇𝐞 −
𝟒𝟐 𝒏𝟐
𝟏 𝟏
• 1st Lyman Series ഥ
𝝂𝑳𝟏 = 𝟒𝑹𝑯𝒆 −
𝟏𝟐 𝒏𝟐
𝟏 𝟏
• 2nd Lyman Series ഥ
𝝂𝑳𝟐 = 𝟒𝑹𝑯𝒆 𝟐 −
𝟐 𝒏𝟐
Energy levels of the H, He+ and Li2+
Transitions in He+ hydrogen like ion
Wavelengths 𝜆12 first Lyman lines, i.e. the spectral lines
with n' = 1, n = 2, of hydrogen and hydrogen-like atomic
ions.
 Bohr’s Correspondence Principle specific for orbits
of hydrogen atom
• The frequency of the radiation emitted fclassical is equal to the orbital frequency forb
of the electron around the nucleus.

• The frequency of the transition from n + 1 to n is

• For very large n only,

Substitute for E0:

From this idea he actually figured angular momentum needs to be 56

quantized in units of for the mathematics to work out
 Excitation of Quantum Jumps by Collisions
• Franck and Hertz showed for the first time in 1913 that the
existence of discrete energy levels in atoms can be
demonstrated with the help of electron collision processes
independently of optical-spectroscopic results.
 Muonic Atoms
• With the simple Bohr model, the muonic atoms, first observed in
1952, can be described.
• They contain, instead of an electron, the 207-times heavier μ
meson or muon and are, in contrast to the Rydberg atoms,
extremely small, in extreme cases hardly larger than the typical
diameter of an atomic nucleus.
• Production of Muons:
• 𝑝 + 𝑛 ⟶ 𝑛 + 𝑛 + 𝜋 + 𝑜𝑟 𝑝 + 𝑛 → 𝑝 + 𝑝 + 𝜋 −
• Pions have a charge +e or -e and mass 𝑚𝜋 = 273 𝑚0 . They decay
into other particles, the muons, according to the reactions
• 𝜋 + → 𝜇+ + 𝜈𝜇 𝑜𝑟 𝜋 − → 𝜇− + 𝜈𝜇ҧ
• The half-life for this decay is 𝑇1/2 = 2.5 × 10−8 𝑠.
• Muons may be characterised as heavy electrons; they have a
charge e, a mass equal to 206.8 𝑚0 , and a half-life 𝑇1/2 = 2.2 ×
10−6 𝑠
• Muons decay into electrons or into positrons.
 𝑍 2 𝑒 4 𝑚0 1
• Energy 𝐸𝑛 = − ∙
32𝜋2 𝜀02 ℏ2 𝑛2
𝑛2 ℏ2 4𝜋𝜀0
• Orbital radius: 𝑟𝑛 = ,
𝑍𝑒 2 𝑚𝜇
• The muon is thus much closer to the nucleus than the
electron.
 Rydberg Atoms
• When the outer electron of an atom is excited into a very
high energy level, it enters a spatially extended orbit - an
orbital - which is far outside the orbitals of all the other
electrons.
• The excited electron then "sees" an atomic core, consisting
of the nucleus and all the inner electrons, which has a
charge +e, just the same as the charge of the hydrogen
nucleus.
• As long as the excited electron does not approach the core
too closely, it behaves as though it belonged to a hydrogen
atom.
• Rydberg atoms behave therefore in many respects like
highly excited hydrogen atoms.
Some properties of Rydberg atoms