 Hydrogen Spectrum introduction

We all know that electrons in an atom or a molecule absorb energy and get excited, they jump
from a lower energy level to a higher energy level and they emit radiation when they come back
to their original states. This phenomenon accounts for the emission spectrum through hydrogen
too, better known as the hydrogen emission spectrum.

In the late 1800s, it was known that when a gas is excited using an electric discharge and the
light emitted is viewed through a diffraction grating; the spectrum observed consists not of a
continuous band of light, but of individual lines with well-defined wavelengths. Experiments
have shown that the wavelengths of the lines were characteristic of the chemical element
emitting the light. They were an atomic fingerprint which resulted from the internal structure of
the atom.

 What is Hydrogen spectrum?

The hydrogen spectrum is an important piece of evidence to show the quantized electronic
structure of an atom. The hydrogen atoms of the molecule dissociate as soon as an electric
discharge is passed through a gaseous hydrogen molecule. It results in the emission of
electromagnetic radiation initiated by the energetically excited hydrogen atoms. The hydrogen
emission spectrum comprises radiation of discrete frequencies. These series of radiation are
named after the scientists who discovered them.

 Hydrogen spectrum wavelength

When a hydrogen atom absorbs a photon, it causes the electron to experience a transition to a
higher energy level, for example, n = 1, n = 2. When a photon is emitted through a hydrogen
atom, the electron undergoes a transition from a higher energy level to a lower, for example, n =
3, n = 2. During this transition from a higher level to a lower level, there is the transmission of
light occurs. The quantized energy levels of the atoms, cause the spectrum to comprise
wavelengths that reflect the differences in these energy levels. For example, the line at 656 nm
corresponds to the transition n = 3 n = 2.

Hydrogen transitions

 Hydrogen emission spectrum:

In the year 1885, on the basis of experimental observations, Balmer proposed the formula for
correlating the wave number of the spectral lines emitted and the energy shells involved. This
formula is given as:
This series of the hydrogen emission spectrum is known as the Balmer series. This is the only
series of lines in the electromagnetic spectrum that lies in the visible region. The value, 109,677
cm-1, is called the Rydberg constant for hydrogen. The Balmer series is basically the part of the
hydrogen emission spectrum responsible for the excitation of an electron from the second shell
to any other shell. Similarly, other transitions also have their own series names. Some of them
are listed below,

 Transition from the first shell to any other shell – Lyman series
 Transition from the second shell to any other shell – Balmer series
 Transition from the third shell to any other shell – Paschen series
 Transition from the fourth shell to any other shell – Bracket series
 Transition from the fifth shell to any other shell – Pfund series

Hydrogen spectrum series

Johannes Rydberg, a Swedish spectroscopist, derived a general formula for the calculation of
wave number of hydrogen spectral line emissions due to the transition of an electron from one
orbit to another. The general formula for the hydrogen emission spectrum is given by:
Where,
n1 = 1,2,3,4 …
n2 = n1 +1
ν= wave number of electromagnetic radiation. The value 109,677 cm-1 is known as Rydberg
constant for hydrogen.

Spectral series are the set of wavelength arranged in sequential fashion. Which
characterises light or any electromagnetic radiation emitted by energised atoms.

Spectrum of Hydrogen gas along with spectral series and respective wavelength.

Hydrogen atom is the simplest atomic system found in nature, thus it produces the simplest of
these series. When the beam of light or any radiation is made to enter the device by passed
through a slit, each individual component of the light or radiation form images of the source.
These images can be visualised when resolved under the spectroscope. The images got will be
in the form of parallel lines arranged next to each other with regular spacing. The lines will be
 apart in higher wavelength side and they come closer gradually when moved from higher to
lower wavelength side. The shortest wavelength will possess least spaced spectral lines and it is
named as series limit.

 BALMER SERIES
The Balmer series is the name given to a series of spectral emission lines of the hydrogen atom that
result from electron transitions from higher levels down to the energy level with principal quantum
number 2. There are four transitions that are visible in the optical waveband that are empirically given
by the Balmer formula. The generalisation of this is the Rydberg formula, which also gives the other
lines of hydrogen outside the optical region of the electromagnetic spectrum:

where is the wavelength, is the Rydberg constant for hydrogen (1.0968 × 10^7 per metre)
and and are integers corresponding to the principal quantum numbers involved in the transition
with > .

The Balmer series of transitions is labelled using Greek characters with representing =
1, representing = 2, etc; the first four transitions are as follows:

=( - ) transition name

( )

1 3-2 H 6563

2 4-2 H 4861

3 5-2 H 4341

4 6-2 H 4102
Because hydrogen is the most abundant element in the Universe, the Balmer lines are a common
feature in optical astronomy and the red H line corresponding to the electron transition from the =
3 to the = 2 energy level gives the characteristic pink/red colour in true-colour images of ionized
regions in planetary nebulae, supernova remnants and stellar nurseries.
 Balmer series of hydrogen lines

 Lyman lines
(hydrogen series from electrons settling from n > 1 to n = 1)

The Lyman series is set of hydrogen ultraviolet spectral lines (Lyman lines) emitted when
an electron descends from an electron shell number n greater than 1 down to n = 1, or the
analogous absorption lines when absorbed electromagnetic radiation makes the electron do the
opposite. It is one of the hydrogen line series, such as the Balmer series and is named after
Theodore Lyman.

 2 -> 1: 121.6 nm (aka Lyman alpha)

 3 -> 1: 102.6 nm
 4 -> 1: 97.3 nm
 5 -> 1: 95.0 nm
 6 -> 1: 93.8 nm
 7 -> 1: 93.1 nm
 8 -> 1: 92.6 nm
 9 -> 1: 92.3 nm
 10 -> 1: 92.1 nm
 11 -> 1: 91.9 nm
  infinity -> 1: Photon
WaveL Freq
91.18 nm Energy
(the Lyman
limit)

Formula for the

wavelengths: 91.18nm 3.3PHz 14eV begin Lyman series

1/wavelength = RH ( 1
- 1/n² )
121.6nm 2.5PHz 10eV end Lyman series
 RH is
the Rydberg
constant for hydrogen, 1.09737316 × 107m-1 = 13.6eV / hc
 n is the higher electron shell number.

A photon at or shorter than the Lyman limit can ionize any hydrogen. Photons from stars that
are shorter than this limit are called Lyman continuum photons or LyC photons. Such
photons are likely to ionize any neutral hydrogen in clouds they pass through, whether the
hydrogen is excited or not. Cases where photons, e.g., from a galaxy, avoid such absorption
(Lyman continuum escape) are of research interest.

 Lyman,hydrogen,line series,lines,spectrum

 Brackett series
(hydrogen lines for electrons settling from n > 4 to n = 4)

The Brackett series is the set of hydrogen spectral lines emitted when an electron descends
from an electron shell number n greater than 4 down to n = 4, or the analogous lines when
absorbed electromagnetic radiation makes the electron do the opposite. It is one of the hydrogen
line series, such as the Lyman series and Balmer series and is named after Frederick Sumner
Brackett.

Lines:

 5 -> 4: 4050 nm
 6 -> 4: 2624 nm
  7 -> 4: 2165 nm
 8 -> 4: 1944 nm
 9 -> 4: 1817 nm
 infinity -> 4: 1458 nm

Formula for the wavelengths:

1/wavelength = RH ( 1/16 - 1/n² )

 RH is the Rydberg constant for hydrogen, 1.09737316 × 107m-1 = 13.6eV / hc

 n is the higher electron shell number.

 Brackett,hydrogen,line series,lines,spectrum

Photon
WaveL Freq
Energy

1458nm 206THz 850meV begin Brackett series

4050nm 74THz 306meV end Brackett series

 Paschen series
(hydrogen lines for electrons settling from n > 3 to n = 3)

The Paschen series is the set of hydrogen spectral lines emitted when an electron descends from
an electron shell number n greater than 3 down to n = 3, or the analogous absorption lines when
absorbed electromagnetic radiation makes the electron do the opposite. It is one of the hydrogen
line series, such as the Lyman series and Balmer series and is named after Friedrich Paschen.
Lines:

 4 -> 3: 1875 nm
 5 -> 3: 1282 nm
 6 -> 3: 1094 nm
 7 -> 3: 1009 nm
 8 -> 3: 995 nm
 9 -> 3: 887 nm
 infinity -> 3: 820 nm

Formula for wavelengths:

1/wavelength = RH ( 1/9 - 1/n² )

 RH is the Rydberg constant for hydrogen, 1.09737316 × 107m-1 = 13.6eV / hc

 n is the higher electron shell number.

Paschen,hydrogen,line series,lines,spectrum

Photon
WaveL Freq
Energy

820nm 366THz 1.6eV begin Paschen series

1875nm 160THz 661meV end Paschen series

 Pfund series

(spectroscopy)
A series of lines in the infrared spectrum of atomic hydrogen whose wave numbers are
given by RH [(1/25) - (1/ n 2)], where RH is the Rydberg constant for hydrogen, and n is any
integer greater than 5.
Atomic Spectra

When an atomic gas or vapour is excited under low pressure by passing an electric
current through it, the spectrum of the emitted radiation has specific wavelengths. It is important
to note that, such a spectrum consists of bright lines on a dark background. This is an emission
line spectrum. Here is an emission line spectrum of hydrogen gas:

λ, vacuum
n
(nm)

6 7460

7 4654

8 3741

9 3297

10 3039

∞ 2279

The emission line spectra work as a ‘fingerprint’ for identification of the gas. Also, on passing a
white light through the gas, the transmitted light shows some dark lines in the spectrum. These
lines correspond to those wavelengths that are found in the emission line spectra of the gas. This
is the absorption spectrum of the material of the gas.

 Atomic Spectra - 'fingerprints' for elements

Electrons exist in energy states within the atom (called orbitals by chemists).
Generally, the further away from the nucleus these states are, the higher the potential energy of
the electron in that state. When an electron is 'free' of the nucleus' influence it is said to have
zero potential energy - a zero energy state. When it is closer to the nucleus it has less potential
energy (needs energy input to escape the influence). It is therefore at a negative energy level
We can put information about these energy states into a diagram

When an electron jumps between energy levels of an atom it either absorbs energy for the
transition or emits a photon when reducing its potential energy.
It can obtain the energy required for 'promotion' to a higher energy state by several means:
photon absorption - absorbing a photon of exactly the correct energy needed for a
'jump'.
obtaining energy by colliding with a free electron. It will take just the amount of
energy it needs for the jump from the free electron's kinetic energy.
an electron can obtain energy from an electrical supply. W = QV, so an electron,
having a charge 'e' will obtain energy of XeV if placed in an potential difference of
X volts.
When absorbing or emitting a photon, the size of that photon's energy depends on the energy
gap between the levels. This is linked to its frequency by the equation
 E = hf
Where
E is the energy of the photon absorbed or emitted -the energy interval between the
energy levels (in joule) [To convert to eV divide by 1.6 x 10-19 ]
h = Planck constant
f = frequency of the photon of electromagnetic radiation (linked to its wavelength
by c = f )
ΔE = hf = hc/λ