Chapter 1: Atomic structure and concept of Quantum mechanics

1. Atomic structure and concept of Quantum mechanics

• Introduction
• Cathode rays and discovery of electron.
• Canal rays and discovery of proton.
• Discovery of neutron.
• Thomson’s model of the atom.
• Rutherford experiment and nuclear atom structure.
• Wave properties and electromagnetic radiation.
• Black body radiation.
• Quantum radiation theory and plank’s constant.
• Atomic spectra of Hydrogen.
• Atomic spectra, absorption spectra, emission spectra.
• The Bohr atomic spectra of Quantum concept.
• Atomic spectra of hydrogen atom according to Bohr model
• Photoelectric effect.
 Chapter 1: Atomic structure and concept of Quantum mechanics
The Structure of the Atom

Dalton imagined an atom that was both extremely small and indivisible.
However, a series of investigations that began in the 1850s and extended into the
twentieth century clearly demonstrated that atoms actually possess internal
structure; that is, they are made up of even smaller particles, which are called
subatomic particles. This research led to the discovery of three such particles
electrons, protons, and neutrons.

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics
Dalton’s Atomic Theory
Dalton’s atomic theory (1808) is based on the following two laws: law of
conservation of mass and law of definite proportions. He also proposed law of
multiple proportions, as a logical consequence of his theory.
1. Every element is composed of extremely small indestructible particles called
atoms (‘atom’ in Greek means indivisible).
2. Atoms of any one element are all similar but they differ from atoms of another
element.
3. Atoms of each element are fundamental particles, have a characteristic mass but
do not have any structure.
4. Atoms of various elements take part in a chemical reaction to form compound
(which is called molecule).
5. In any compound, the relative number and kinds of atoms are constant.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Cathode rays and discovery of electron.
In mid-1800s, scientists (William Crookes 1879, Julius Plucker 1889) started to study the
discharge of electricity through partially evacuated tubes. Gases are normally poor conductor of
electricity and they do not conduct electricity under normal pressure even with an applied
potential of 1000 volt. However when the pressure was reduced to 10-2 at a potential of 1000 volt,
Crookes and Plucker noticed that:
(i) From the cathode surface a glow surrounding the cathode began and the space left between the
glow and cathode was named Crookes dark space. Under this condition electric current starts to
flow from one electrode to other.
(ii) When the pressure is sufficiently low, the glow fills whole of the tube.

Figure 1.1: Cathode ray tube

 Chapter 1: Atomic structure and concept of Quantum mechanics
Important characteristics of cathode rays are as follows:

1. Cathode rays travel in straight lines with high speed of the order of 107 ms−1, producing
shadows of the objects placed in their path.
2. Cathode rays can pass through thin layers of matter.
3. Cathode rays are emitted from the surface of the cathode; their direction is not affected by
the position of the anode.
[Link] rays have high kinetic energy and therefore:
(i) They can exert mechanical pressure on the object on which they fall.
(ii) They can produce heat when stopped by matter.
(iii) They can ionize a gas.
5. Cathode rays are deflected, both, by electric and magnetic fields.
6. Cathode rays produce fluorescence when they fall on certain substances like ZnS. The color
of fluorescence varies with the chemical nature of substance.
7. Cathode rays can produce chemical changes and thus they affect photographic plates.
 Chapter 1: Atomic structure and concept of Quantum mechanics
The Electron
Subsequently Thomson (1897) carried out the discharge through a vacuum tube which was filled with a gas at very
low pressure (10-2 to 10-3 mm); he noticed the emission of invisible rays which produced fluorescence on the glass
and influenced photographic plate. These rays were called cathode rays.
• One device used to investigate this phenomenon was a cathode ray tube (It is a glass tube from
which most of the air has been evacuated).

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics

When the two metal plates are connected to a high-voltage source;

• The negatively charged plate, called the cathode, emits an invisible ray.
• The cathode ray is drawn to the positively charged plate, called the anode,
where it passes through a hole and continues traveling to the other end of the
tube.
• When the ray strikes the specially coated surface, it produces a strong
fluorescence, or bright light.
 Chapter 1: Atomic structure and concept of Quantum mechanics
The Electron
• Two electrically charged plates and a magnet were added to the outside of the
cathode ray tube.
• When the magnetic field is on and the electric field is off, the cathode ray
strikes point A.
• When only the electric field is on, the ray strikes point C.
• When both the magnetic and the electric fields are off or when they are both
on but balanced so that they cancel each other’s influence, the ray strikes point B.
According to electromagnetic theory, a moving
charged body behaves like a magnet and can
interact with electric and magnetic fields
through which it passes.
 Chapter 1: Atomic structure and concept of Quantum mechanics

• Because the cathode ray is attracted by the plate bearing positive charges and
repelled by the plate bearing negative charges, it must consist of negatively
charged particles.
• We know these negatively charged particles as electrons.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Thomson’s Model
After the discovery of protons and electrons, Thomson in 1898 proposed a
watermelon model; the atom is considered as a sphere of positive charge with the
electrons distributed within the sphere of radius of 10−10 m so as to give the most
stable electrostatic agreement. In this model, the atom is visualized as a pudding or
cake of positive charge with raisins (electrons) embedded in it. A major point of this
model is that the mass of atom is considered to be spread uniformly over the atom.
 Chapter 1: Atomic structure and concept of Quantum mechanics

The Discovery of proton

(1908 Nobel Prize

in Chemistry)

Rutherford’s Experiment
1. Atoms positive charge is concentrated in the nucleus
2. Proton (p) has opposite (+) charge of electron (-)
3. Mass of p is 1840x mass of e- (1.67 x 10-24 g)

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics
The following observations were made:
1. Most of the α-particles went straight without suffering any
deflection.
2. Some of them were deflected through small angles.
3. A very small number (about 1 in 20,000) did not pass through
the foil at all but suffered large deflections or even rebound.
Following conclusions were drawn from these observations:

a) Many of the particles went straight through the metal foil undeflected,
indicating that there must be very large empty space within the atom.
b) Some of the α-particles were deflected from their original paths through
moderate angles, indicating that whole of the positive charge is
concentrated in a space called nucleus. It is proposed to be present at the
centre of the atom. Rutherford’s Model of the Atom
c) A very small number of the α-particles suffered strong deflections or even
rebound on their path indicating that the nucleus is rigid and α-particles
recoil due to direct collision with the positively charged heavy mass.
 Chapter 1: Atomic structure and concept of Quantum mechanics

The Discovery of Neutron Chadwick’s Experiment (1932) (1935 Noble Prize in Physics)

• When a thin sheet of beryllium was bombarded with α-particles, a very high-
energy radiation similar to g rays was emitted by the metal.

• Later experiments showed that the rays actually consisted of a third type of
subatomic particles, which Chadwick named neutrons, electrically neutral
particles having a mass slightly greater than that of protons. By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics
Discovery of Neutron and Rutherford’s Model
Chadwick bombarded beryllium with a stream of α-particles. He observed that the produced
penetrations were not affected by electric and magnetic fields. These radiations consisted of
neutral particles, which were called neutrons.

The mass of the neutron was determined to be 1.675 × 10−24 g, that is, nearly equal to the mass
of proton.
Thus a neutron is a subatomic particle having a mass of 1.675 × 10−24 g, approximately 1 amu
or nearly equal to the mass of proton or hydrogen atom and carrying no electrical charge. The
e/m of neutron is zero.
 Chapter 1: Atomic structure and concept of Quantum mechanics

Rutherford’s Model of Atom: Rutherford proposed a model of the atom known as nuclear
atomic model. As per this model,

a) An atom consists of a positively charged heavy nucleus where all the protons and neutrons are present. The
number of the positive charge on the nucleus is different for different atoms.
b) The volume of the nucleus is very small and is only a very small fraction of the total volume of the atoms.

Thus, the diameter of an atom is 100,000 times the diameter of the nucleus. The radius of a nucleus is proportional to
the cube root of the mass number. Radius of the nucleus = 1.33 × 10−13 × A1/3 cm where A is the mass number.
c) There is an empty space around nucleus called extra nuclear part, where electrons are present. The number of
electrons in an atom is always equal to the number of protons present in the nucleus. The volume of the atom is
about 1015 times the volume of the nucleus.

d) The electrons revolve around the nucleus in closed orbits with high speeds. Centrifugal force is acting on the
revolving electrons and is being counterbalanced by the force of attraction between electrons and the nucleus.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Drawbacks of Rutherford’s Model
According to wave theory, when a charged particle moves under the influence of
an attractive force, it loses energy continuously in the form of electromagnetic
radiations. Thus, the electron which moves in an attractive field (created by
protons present in the nucleus) will emit radiations. As result the electron will lose
energy at every turn and move closer and closer to the nucleus following a spiral
path and finally fall into the nucleus, thereby making the atom unstable. But the
atom is quite stable meaning the electrons do not fall into nucleus, thus this Figure1.4 : Spiral path of
electron
model does not explain the stability of the atom.
1. If the electrons lose energy continuously, the observed spectra should be
continuous. But the observed spectra consists of well-defined lines of definite
frequency. Hence, in an atom, the loss of energy by the electrons is not continuous.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Wave properties and electromagnetic radiation.
Properties of Waves:
The fundamental properties of waves are illustrated in
Figure 1.6 Waves are characterized by their wavelength,
frequency, and amplitude. Wavelength λ (lambda) is the
distance between identical points on successive waves (e.g.,
successive peaks or successive troughs). The frequency ν
(nu) is the number of waves that pass through a particular
point in 1 second. Amplitude is the vertical distance from
the midline of a wave to the top of the peak or the bottom of
the trough. The speed of a wave depends on the type of
wave and the nature of the medium through which the
wave is traveling (e.g. air, water, or a vacuum).
The speed of light through a vacuum, c, is 2.99792458 × 108 Figure 1.6: Characteristics of
m/s. The speed, wavelength, and frequency of a wave are waves: wavelength, amplitude, and
related by the equation Equation 1.1 c = λv frequency.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Equation 1.1 c = λv
where λ and v are expressed in meters (m) and reciprocal seconds (s−1), respectively.

Figure 1.7 Electromagnetic spectrum. Each type of radiation is spread over a

specific range of wavelengths (and frequencies). Visible light ranges from 400 nm
(violet) to 700 nm (red).
 Chapter 1: Atomic structure and concept of Quantum mechanics
The Electromagnetic Spectrum
In 1873 James Clerk Maxwell, a Scottish physicist and mathematician, proposed
that visible light consisted of electromagnetic waves.
According to Maxwell’s theory, an electromagnetic wave has two things:
1. An electric field component.
2. A magnetic field component.
These two components have the same wavelength and frequency, and hence the
same speed, but they travel in mutually perpendicular planes (Figure 1.8).
Maxwell’s theory provides a mathematical description of the general behavior
of light; and describes accurately how energy in the form of radiation can be
propagated through space as oscillating electric and magnetic fields.
 Chapter 1: Atomic structure and concept of Quantum mechanics

Figure 1.8 Electric field and magnetic field components of an electromagnetic

wave. These two components have the same wavelength, frequency, and
amplitude, but they vibrate in two mutually perpendicular planes.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Quantum Theory

Early attempts by nineteenth-century physicists to figure out the structure of the

atom met with only limited success. This was largely because they were attempting
to understand the inner workings of atoms using the laws of classical physics,
which describe the behavior of macroscopic objects.

• It took a long time to realize—and an even longer time to accept—that the

behavior of subatomic particles is not governed by the same physical laws as
larger objects.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Quantization of Energy
When a solid is heated, it emits electromagnetic radiation, known as blackbody radiation, over a
wide range of wavelengths. The red glow of the element of an electric stove and the bright
white light of a tungsten lightbulb are examples of blackbody radiation.
• Measurements taken in the latter part of the nineteenth century showed that the amount of
energy given off by an object at a certain temperature depends on the wavelength of the
emitted radiation.
• Attempts to account for this dependence in terms of established wave theory and
thermodynamic laws were only partially successful.
• One theory was able to explain short-wavelength dependence but failed to account for the
longer wavelengths.
• Another theory accounted for the longer wavelengths but failed for short wavelengths.
• With no one theory that could explain both observations, it seemed that something
fundamental was missing from the laws of classical physics.

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics
Max Planck in 1900, German physicist provided an idea that departed drastically from accepted
concepts. Classical physics assumed that radiant energy was continuous; that is, it could be
emitted or absorbed in any amount.
• Based on data from blackbody radiation experiments, Planck proposed that radiant energy
could be emitted or absorbed only in discrete quantities.
• Planck gave the name quantum to the smallest quantity of energy that can be emitted (or
absorbed) in the form of electromagnetic radiation. The energy E of a single quantum of
energy is given by Equation 1.2 :
E = hv
where h is called Planck’s constant and v is the frequency of the radiation.
The value of Planck’s constant is 6.63 × 10−34 J · s.
According to quantum theory, energy is always emitted in whole-number multiples of hv. At the
time Planck presented his theory, he could not explain why energies should be fixed or
quantized in this manner. Starting with this hypothesis, however, he had no difficulty
correlating the experimental data for the emission by solids over the entire range of wavelengths;
the experimental data supported his new quantum theory. By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics
Photons and the Photoelectric Effect
In 1905, Albert Einstein used the theory to explain another physical phenomenon, the
photoelectric effect.
In the photoelectric effect, electrons are ejected from the surface of a metal exposed to light.
However, the light must be of a certain minimum frequency, called the threshold frequency
(Figure1.9). The number of electrons ejected was proportional to the intensity (or brightness) of
the light, but the energies of the ejected electrons were not.
Below the threshold frequency no electrons were ejected no matter how intense the light.
The photoelectric effect could not be explained by the wave theory of light, which associated the
energy of light with its intensity. Einstein, however, made an extraordinary assumption, he
suggested that a beam of light is really a stream of particles. These “particles” of light are now
called photons. Using Planck’s quantum theory of radiation as a starting point, Einstein deduced
that each photon must possess energy E given by the equation 1.3:

Ephoton = hv where h is Planck’s constant and v is the frequency of the light

 Chapter 1: Atomic structure and concept of Quantum mechanics

Figure 1.9 Apparatus for studying the photoelectric effect. Light of a certain frequency falls on a
clean metal surface. Ejected electrons are attracted toward the positive electrode. The flow of
electrons is registered by a detecting meter.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Electrons are held in a metal by attractive forces, and so removing them from the metal requires
light of a sufficiently high frequency to break them free. Shining a beam of light onto a metal
surface can be thought of as shooting a beam of particles—photons—at the metal atoms.
• If the frequency of the photons is such that hv exactly equals the energy that binds the
electrons in the metal, then the light will have just enough energy to knock the electrons
loose.
• If we use light of a higher frequency, then not only will the electrons be knocked loose, but
they will also acquire some kinetic energy. This situation is summarized by the equation 1.4

hv = KE + W Equation 1.4

where KE is the kinetic energy of the ejected electron and W is the binding energy of the electron
in the metal. Rewriting Equation 1.5 as
KE = hv − W
 Chapter 1: Atomic structure and concept of Quantum mechanics
Shows that the more energetic the photon (i.e., the higher its frequency), the greater the kinetic
energy of the ejected electron.
Ø If the frequency of light is below
• If the frequency of light is below the threshold frequency, the photon will simply bounce off
the surface and no electrons will be ejected.
Ø If the frequency is equal to the threshold frequency
• If the frequency is equal to the threshold frequency, it will dislodge the most loosely held
electron.
Ø If the frequency is above the threshold frequency
• If the frequency is above the threshold frequency, it will not only dislodge the electron, but also
impart certain kinetic energy to the ejected electron.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Bohr’s Theory of the Hydrogen Atom
In the seventeenth century, Newton had shown that sunlight is composed of various color
components that can be recombined to produce white light. Since that time, chemists and
physicists have studied the characteristics of such emission spectra. The emission spectrum of a
substance can be seen by energizing a sample of material with either thermal energy or some
other form of energy (such as a high-voltage electrical discharge if the substance is a gas). A “red-
hot” or “white-hot” iron bar freshly removed from a fire produces a characteristic glow. The glow
is the visible portion of its emission spectrum. The heat given off by the same iron bar is
another portion of its emission spectrum the infrared region. A feature common to the
emission spectrum of the sun and that of a heated solid is that both are continuous; that is, all
wavelengths of visible light are present in each spectrum (Figure 1.10).
 Chapter 1: Atomic structure and concept of Quantum mechanics

(a) (b)

Figure 1.10 The visible white light emitted by (a) the sun and (b) a white-hot iron bar. In each
case, the white light is the combination of all visible wavelengths.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Atomic spectra of Hydrogen
The impression produced on a screen when radiations of particular wavelengths are passed
through a prism or diffraction grating is known as spectrum. It is broadly of two types:
1. Emission spectra and 2. Absorption spectra
Differences between emission spectrum and absorption spectrum
Emission spectrum Absorptions spectrum
1. It gives bright lines (colored on 1. It gives dark lines on the bright
the dark background. background.
2. Radiations from emitting source 2. It is observed when the white
are analyzed by the spectroscope. light is passed through the
3. It may be continuous (if source substance and the transmitted
emits white light) and may be radiations are analyzed by the
discontinuous (if the source emits spectroscope. Figure 2.5: Continuous spectrum
colored light). 3. These are always discontinuous.
 Chapter 1: Atomic structure and concept of Quantum mechanics
Emission Spectra
It is obtained from the substances which emit light on excitation, that is, either by heating the
substances on a film or by passing electric discharge through a thin filament of high melting
point metal. Emission spectra are of two types:
(a) Continuous spectra: When white light is allowed to pass through a prism, the light gets
resolved into several colours. This spectrum is a rainbow of colours, meaning violet merges into
blue, blue into green and so on. This is a continuous spectrum.
(b) Discontinuous spectra: When gases or vapours of a chemical substance are heated in an
electric arc or in a Bunsen flame, light is emitted. When a ray of this light is passed through a
prism, a line spectrum is produced.
 Chapter 1: Atomic structure and concept of Quantum mechanics

Atomic Line Spectra

• Unlike those of the sun or a white-hot iron bar, the emission spectra of atoms in the gas phase
do not show a continuous spread of wavelengths from red to violet; rather, the atoms produce
bright lines in distinct parts of the visible spectrum. A line spectrum is the emission of light only
at specific wavelengths. Figure 1.11 is a schematic diagram of a discharge tube that is used to
study emission spectra.
• Every element has a unique emission spectrum, so the characteristic lines in atomic spectra
can be used in chemical analysis to identify elements, much as fingerprints are used to
identify people. When the lines of the emission spectrum of a known element exactly match
the lines of the emission spectrum of an unknown sample, the identity of the element in the
sample is established. Although the procedure of identifying elements by their line spectra had
been used for many years in chemical analysis, the origin of the spectral lines was not
understood until early in the twentieth century.

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics

Figure 1.11 (a) Experimental arrangement for studying the emission spectra of atoms and
molecules. The gas being studied is in a discharge tube containing two electrodes. As electrons
flow from the negative electrode to the positive electrode, they collide with the gas particles. The
collisions lead to the emission of light by the atoms (or molecules). The emitted light is separated
into its components by a prism. (b) Visible line emission spectrum of hydrogen.
 Chapter 1: Atomic structure and concept of Quantum mechanics

In 1885, Johann Balmer developed a simple equation that could be used to calculate
the wavelengths of the four visible lines in the emission spectrum of hydrogen.
Johannes Rydberg developed Balmer’s equation further, yielding an equation that
could calculate not only the visible wavelengths, but those of all hydrogen’s spectral
lines:

The Rydberg equation, λ is the wavelength of a line in the spectrum; R∞ is the

Rydberg constant (1.09737316 × 107 m−1); and n1 and n2 are positive integers,
where n2>n1.
By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics

The Line Spectrum of Hydrogen

In 1913, not long after Planck’s and Einstein’s discoveries, a theoretical explanation
of the emission spectrum of the hydrogen atom was presented by Danish physicist
Niels Bohr. Bohr’s treatment is very complex and is no longer considered to be
correct in all its details. We will concentrate only on his important assumptions
and final results, which account for the observed spectral lines and which provide
an important step toward the understanding of quantum theory.

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics

When Bohr first approached this problem, physicists already knew that the atom contains

electrons and protons. They thought of an atom as an entity in which electrons whirled around the

nucleus in circular orbits at high velocities. This was an appealing description because it

resembled the familiar model of planetary motion around the sun. However, according to the laws

of classical physics, an electron moving in an orbit of a hydrogen atom would experience an

acceleration toward the nucleus by radiating away energy in the form of electromagnetic waves.

Thus, such an electron would quickly spiral into the nucleus and annihilate itself with the proton.

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics

To explain why this does not happen, Bohr postulated that the electron is allowed to occupy
only certain orbits of specific energies. In other words, the energies of the electron are
quantized. An electron in any of the allowed orbits will not radiate energy and therefore will
not spiral into the nucleus. Bohr attributed the emission of radiation by an energized hydrogen
atom to the electron dropping from a higher-energy orbit to a lower one and giving up a quantum
of energy (a photon) in the form of light (Figure 1.12). Using arguments based on electrostatic
interaction and Newton’s laws of motion, Bohr showed that the energies that the electron in the
hydrogen atom can possess are given by the equation 1.5

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics

where n is an integer with values n = 1, 2, 3, and so on. The negative sign in

Equation 1.5 is an arbitrary convention, signifying that the energy of the electron in
the atom is lower than the energy of a free electron, which is an electron that is
infinitely far from the nucleus. The energy of a free electron is arbitrarily assigned a
value of zero. Mathematically, this corresponds to setting n equal to infinity in
Equation:
Equation 1.5

By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics
Each line in the
visible emission
spectrum of hydrogen
is the result of an
electronic transition
from a higher excited
state (n = 3, 4, 5, or 6)
to a lower excited
state (n = 2). The
energy gap between
the initial and final
states determines the
wavelength of the
light emitted.

Figure 1.12: Emission spectrum of hydrogen. By Dr. Naktal

 Chapter 1: Atomic structure and concept of Quantum mechanics

• As the electron gets closer to the nucleus (as n decreases), En becomes larger in absolute value,
but also more negative. The most negative value, then, is reached when n = 1, which
corresponds to the most stable energy state.
• We call this the ground state, the lowest energy state of an atom. The stability of the electron
diminishes as n increases. Each energy state in which n > 1 is called an excited state. Each
excited state is higher in energy than the ground state.
• In the hydrogen atom, an electron for which n is greater than 1 is said to be in an excited state.
The radius of each circular orbit in Bohr’s model depends on n . Thus, as n increases from 1 to
2 to 3, the orbit radius increases very rapidly.
• The higher the excited state, the farther away the electron is from the nucleus (and the less
tightly held it is by the nucleus). By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics

• Bohr’s theory enables us to explain the line spectrum of the hydrogen atom. Radiant energy
absorbed by the atom causes the electron to move from the ground state (n = 1) to an excited
state (n > 1).
• Conversely, radiant energy (in the form of a photon) is emitted when the electron moves from a
higher-energy excited state to a lower-energy excited state or the ground state.
• The journey from a lower step to a higher one is an energy-requiring process, whereas
movement from a higher step to a lower step is an energy-releasing process.
• The quantity of energy involved in either type of change is determined by the distance between
the beginning and ending steps. Similarly, the amount of energy needed to move an electron in
the Bohr atom depends on the difference in energy levels between the initial and final states.
By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics
To apply Equation 1.5 to the emission process in a hydrogen atom, let us suppose that the electron
is initially in an excited state characterized by ni. During emission, the electron drops to a lower
energy state characterized by nf (the subscripts i and f denote the initial and final states,
respectively). This lower energy state may be the ground state, but it can be any state lower than
the initial excited state. The difference between the energies of the initial and final states is
Because this transition results in the emission of a photon of
frequency v and energy hv, we can write

A photon is emitted when ni > nf. Consequently, the term in

parentheses is positive, making ΔE negative (energy is lost to the
surroundings). A photon is absorbed when nf > ni, making the term
in parentheses negative, so ΔE is positive. Each spectral line in the
emission spectrum of hydrogen corresponds to a particular
transition in a hydrogen atom.
By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics

When we study a large number of hydrogen atoms, we observe all possible transitions and hence
the corresponding spectral lines. The brightness of a spectral line depends on how many
photons of the same wavelength are emitted.
To calculate the wavelength of an emission line, we substitute c/λ for v and then divide both sides
of Equation 3.8 by hc. In addition, because wavelength can have only positive values, we take the
absolute value of the right side of the equation. (In this case, we do so simply by eliminating the
negative sign.)
By Dr. Naktal
 Chapter 1: Atomic structure and concept of Quantum mechanics
The emission spectrum of hydrogen includes a wide range of wavelengths from the infrared to the
ultraviolet. Table 3.1 lists the series of transitions in the hydrogen spectrum, each with a different
value of nf. The series are named after their discoverers (Lyman, Balmer, Paschen, and Brackett).
The Balmer series was the first to be studied because some of its lines occur in the visible region.
Figure 1.13 shows transitions associated with spectral lines in each of the emission series. Each
horizontal line represents one of the allowed energy levels for the electron in a hydrogen atom.
The energy levels are labeled with their n values.

Figure1.13 Energy levels in the

hydrogen atom and the various
emission series. Each series
terminates at a different value of n.

By Dr. Naktal
Chapter 1: Atomic structure and concept of Quantum mechanics

The End

By Dr. Naktal