Chapter 2: Structure of Atom

Objectives

After studying this unit, you will be able to:

●​ Understand the discovery of electrons, protons, and neutrons and their characteristics.
●​ Describe Thomson, Rutherford, and Bohr atomic models.
●​ Understand the important features of the quantum mechanical model of the atom.
●​ Understand the nature of electromagnetic radiation and Planck's quantum theory.
●​ Explain the photoelectric effect and describe features of atomic spectra.
●​ State the de Broglie relation and Heisenberg uncertainty principle.
●​ Define an atomic orbital in terms of quantum numbers.
●​ State the Aufbau principle, Pauli exclusion principle, and Hund's rule of maximum
multiplicity.
●​ Write the electronic configurations of atoms.

Introduction

The rich diversity of chemical behavior of different elements can be traced to the differences in
the internal structure of atoms of these elements. The existence of atoms has been proposed
since the time of early Indian and Greek philosophers (400 B.C.), who viewed atoms as the
fundamental building blocks of matter. The word 'atom' is derived from the Greek word 'a-tomio,'
which means 'uncuttable' or 'non-divisible.' These earlier ideas were mere speculations and
could not be tested experimentally. The atomic theory of matter was first proposed on a firm
scientific basis by John Dalton, a British school teacher, in 1808. Dalton's atomic theory
regarded the atom as the ultimate particle of matter and successfully explained the law of
conservation of mass, the law of constant composition, and the law of multiple proportions.
However, it failed to explain the results of many experiments, such as the electrical charging of
substances like glass or ebonite when rubbed with silk or fur.

Discovery of Sub-Atomic Particles

An insight into the structure of the atom was obtained from experiments on electrical discharge
through gases. Before discussing these results, it is important to keep in mind a basic rule
regarding the behavior of charged particles: "Like charges repel each other, and unlike charges
attract each other."

Discovery of Electron

In 1830, Michael Faraday showed that if electricity is passed through a solution of an electrolyte,
chemical reactions occur at the electrodes, resulting in the liberation and deposition of matter at
the electrodes. These results suggested the particulate nature of electricity. In the mid-1850s,
many scientists, mainly Faraday, began to study electrical discharge in partially evacuated
tubes, known as cathode ray discharge tubes. A cathode ray tube is made of glass containing
two thin pieces of metal called electrodes sealed in it. The electrical discharge through the
gases could be observed only at very low pressures and very high voltages. When a sufficiently
high voltage is applied across the electrodes, current starts flowing through a stream of particles
moving in the tube from the negative electrode (cathode) to the positive electrode (anode).
These were called cathode rays or cathode ray particles.

The results of these experiments are summarized below:

1.​ The cathode rays start from the cathode and move towards the anode.
2.​ These rays themselves are not visible, but their behavior can be observed with the help
of certain kinds of materials (fluorescent or phosphorescent) that glow when hit by them.
3.​ In the absence of an electrical or magnetic field, these rays travel in straight lines.
4.​ In the presence of an electrical or magnetic field, the behavior of cathode rays is similar
to that expected from negatively charged particles, suggesting that the cathode rays
consist of negatively charged particles called electrons.
5.​ The characteristics of cathode rays (electrons) do not depend on the material of the
electrodes and the nature of the gas present in the cathode ray tube.

Thus, we can conclude that electrons are basic constituents of all atoms.

Charge to Mass Ratio of Electron

In 1897, British physicist J.J. Thomson measured the ratio of electrical charge (e) to the mass of
the electron (me) by using a cathode ray tube and applying electrical and magnetic fields
perpendicular to each other as well as to the path of the electrons. Thomson argued that the
amount of deviation of the particles from their path in the presence of an electrical or magnetic
field depends upon:

1.​ The magnitude of the negative charge on the particle: the greater the magnitude of the
charge on the particle, the greater the interaction with the electric or magnetic field, and
thus the greater the deflection.
2.​ The mass of the particle: the lighter the particle, the greater the deflection.
3.​ The strength of the electrical or magnetic field: the deflection of electrons from their
original path increases with the increase in the voltage across the electrodes or the
strength of the magnetic field.

By carrying out accurate measurements on the amount of deflections observed by the electrons
on the electric field strength or magnetic field strength, Thomson was able to determine the
value of e/me as:

eme=1.758820×1011 C kg−1 \frac{e}{m_{e}} = 1.758820 \times 10^{11} \, \text{C

kg}^{-1}me​e​=1.758820×1011C kg−1

where me is the mass of the electron in kg, and e is the magnitude of the charge on the electron
in coulombs (C). Since electrons are negatively charged, the charge on the electron is -e.
Charge on the Electron

R.A. Millikan (1868-1953) devised a method known as the oil drop experiment (1906-14) to
determine the charge on the electrons. He found the charge on the electron to be -1.6 x 10^-19
C. The present accepted value of the electrical charge is -1.602176 x 10^-19 C. The mass of the
electron (me) was determined by combining these results with Thomson's value of the e/me
ratio.

me=ee/me=1.602176×10−19 C1.758820×1011 C kg−1=9.1094×10−31 kg m_{e} = \frac{e}{e /

m_{e}} = \frac{1.602176 \times 10^{-19} \, \text{C}}{1.758820 \times 10^{11} \, \text{C kg}^{-1}} =
9.1094 \times 10^{-31} \, \text{kg}me​=e/me​e​=1.758820×1011C
kg−11.602176×10−19C​=9.1094×10−31kg

Discovery of Protons and Neutrons

Electrical discharge carried out in the modified cathode ray tube led to the discovery of canal
rays carrying positively charged particles. The characteristics of these positively charged
particles are listed below:

1.​ Unlike cathode rays, the mass of positively charged particles depends upon the nature
of the gas present in the cathode ray tube. These are simply the positively charged
gaseous ions.
2.​ The charge-to-mass ratio of the particles depends on the gas from which these originate.
3.​ Some of the positively charged particles carry a multiple of the fundamental unit of
electrical charge.
4.​ The behavior of these particles in a magnetic or electrical field is opposite to that
observed for electrons or cathode rays.

The smallest and lightest positive ion was obtained from hydrogen and was called a proton. This
positively charged particle was characterized in 1919. Later, a need was felt for the presence of
an electrically neutral particle as one of the constituents of the atom. These particles were
discovered by Chadwick (1932) by bombarding a thin sheet of beryllium with alpha particles.
When electrically neutral particles having a mass slightly greater than that of protons were
emitted, he named these particles neutrons. The important properties of all these fundamental
particles are given in Table 2.1.

Atomic Models

Observations obtained from the experiments mentioned in the previous sections suggested that
Dalton's indivisible atom is composed of sub-atomic particles carrying positive and negative
charges. The major problems before scientists after the discovery of sub-atomic particles were:

●​ To account for the stability of the atom.

●​ To compare the behavior of elements in terms of both physical and chemical properties.
 ●​ To explain the formation of different kinds of molecules by the combination of different
atoms.
●​ To understand the origin and nature of the characteristics of electromagnetic radiation
absorbed or emitted by atoms.

Different atomic models were proposed to explain the distributions of these charged particles in
an atom. Although some of these models were not able to explain the stability of atoms, two of
these models, one proposed by J.J. Thomson and the other proposed by Ernest Rutherford, are
discussed below.

Thomson Model of Atom

J.J. Thomson, in 1898, proposed that an atom possesses a spherical shape (radius
approximately 10^-10 m) in which the positive charge is uniformly distributed. The electrons are
embedded into it in such a manner as to give the most stable electrostatic arrangement. This
model can be visualized as a pudding or watermelon of positive charge with plums or seeds
(electrons) embedded into it. An important feature of this model is that the mass of the atom is
assumed to be uniformly distributed over the atom. Although this model was able to explain the
overall neutrality of the atom, it was not consistent with the results of later experiments.
Thomson was awarded the Nobel Prize for physics in 1906 for his theoretical and experimental
investigations on the conduction of electricity by gases.

Rutherford's Nuclear Model of Atom

Rutherford and his students (Hans Geiger and Ernest Marsden) bombarded very thin gold foil
with alpha particles. Rutherford's famous alpha-particle scattering experiment is represented in
Fig. 2.5. A stream of high-energy alpha particles from a radioactive source was directed at a thin
foil (thickness ~100 nm) of gold metal. The thin gold foil had a circular fluorescent zinc sulfide
screen around it. Whenever alpha particles struck the screen, a tiny flash of light was produced
at that point.

The results of the scattering experiment were quite unexpected. According to Thomson's model
of the atom, the mass of each gold atom in the foil should have been spread evenly over the
entire atom, and alpha particles had enough energy to pass directly through such a uniform
distribution of mass. It was expected that the particles would slow down and change directions
only by small angles as they passed through the foil. It was observed that:

1.​ Most of the alpha particles passed through the gold foil undeflected.
2.​ A small fraction of the alpha particles was deflected by small angles.
3.​ A very few alpha particles (~1 in 20,000) bounced back, i.e., were deflected by nearly
180°.

On the basis of the observations, Rutherford drew the following conclusions regarding the
structure of the atom:
 1.​ Most of the space in the atom is empty as most of the alpha particles passed through the
foil undeflected.
2.​ A few positively charged alpha particles were deflected. The deflection must be due to
an enormous repulsive force showing that the positive charge of the atom is not spread
throughout the atom as Thomson had presumed. The positive charge has to be
concentrated in a very small volume that repelled and deflected the positively charged
alpha particles.
3.​ Calculations by Rutherford showed that the volume occupied by the nucleus is negligibly
small as compared to the total volume of the atom. The radius of the atom is about
10^-10 m, while that of the nucleus is 10^-15 m. One can appreciate this difference in
size by realizing that if a cricket ball represents a nucleus, then the radius of the atom
would be about 5 km.

On the basis of the above observations and conclusions, Rutherford proposed the nuclear
model of the atom. According to this model:

1.​ The positive charge and most of the mass of the atom are densely concentrated in an
extremely small region. This very small portion of the atom was called the nucleus by
Rutherford.
2.​ The nucleus is surrounded by electrons that move around the nucleus with very high
speed in circular paths called orbits. Thus, Rutherford's model of the atom resembles the
solar system in which the nucleus plays the role of the sun and the electrons that of
revolving planets.
3.​ Electrons and the nucleus are held together by electrostatic forces of attraction.

Atomic Number and Mass Number

The presence of a positive charge on the nucleus is due to the protons in the nucleus. As
established earlier, the charge on the proton is equal but opposite to that of the electron. The
number of protons present in the nucleus is equal to the atomic number (Z). For example, the
number of protons in the hydrogen nucleus is 1, in the sodium atom it is 11, therefore their
atomic numbers are 1 and 11, respectively. In order to keep the electrical neutrality, the number
of electrons in an atom is equal to the number of protons (atomic number, Z). For example, the
number of electrons in the hydrogen atom and sodium atom are 1 and 11, respectively.

Atomic number (Z)=number of protons in the nucleus of an atom=number of electrons in a

neutral atom \text{Atomic number (Z)} = \text{number of protons in the nucleus of an atom} =
\text{number of electrons in a neutral atom}Atomic number (Z)=number of protons in the nucleus
of an atom=number of electrons in a neutral atom

While the positive charge of the nucleus is due to protons, the mass of the nucleus is due to
protons and neutrons. As discussed earlier, protons and neutrons present in the nucleus are
collectively known as nucleons. The total number of nucleons is termed as the mass number (A)
of the atom.
Mass number (A)=number of protons (Z)+number of neutrons (n) \text{Mass number (A)} =
\text{number of protons (Z)} + \text{number of neutrons (n)}Mass number (A)=number of protons
(Z)+number of neutrons (n)

Isobars and Isotopes

The composition of any atom can be represented by using the normal element symbol (X) with a
superscript on the left-hand side as the atomic mass number (A) and a subscript (Z) on the
left-hand side as the atomic number (i.e., AZX\frac{A}{Z} XZA​X).

Isobars are atoms with the same mass number but different atomic numbers, for example,
146C\frac{14}{6} C614​C and 147N\frac{14}{7} N714​N. On the other hand, atoms with identical
atomic numbers but different atomic mass numbers are known as isotopes. In other words,
according to equation 2.4, it is evident that the difference between the isotopes is due to the
presence of different numbers of neutrons present in the nucleus. For example, considering the
hydrogen atom again, 99.985% of hydrogen atoms contain only one proton. This isotope is
called protium (11H\frac{1}{1} H11​H). The rest of the percentage of hydrogen atoms contain two
other isotopes: one containing 1 proton and 1 neutron is called deuterium (21D\frac{2}{1} D12​D,
0.015%), and the other one possessing 1 proton and 2 neutrons is called tritium (31T\frac{3}{1}
T13​T). The latter isotope is found in trace amounts on Earth. Other examples of commonly
occurring isotopes are carbon atoms containing 6, 7, and 8 neutrons besides 6 protons
(126C,136C,146C\frac{12}{6} C, \frac{13}{6} C, \frac{14}{6} C612​C,613​C,614​C); chlorine atoms
containing 18 and 20 neutrons besides 17 protons (3517Cl,3717Cl\frac{35}{17} Cl, \frac{37}{17}
Cl1735​Cl,1737​Cl).

An important point to mention regarding isotopes is that the chemical properties of atoms are
controlled by the number of electrons, which are determined by the number of protons in the
nucleus. The number of neutrons present in the nucleus has very little effect on the chemical
properties of an element. Therefore, all the isotopes of a given element show the same
chemical behavior.

Drawbacks of Rutherford Model

As you have learned above, Rutherford's nuclear model of an atom is like a small-scale solar
system with the nucleus playing the role of the massive sun and the electrons being similar to
the lighter planets. When classical mechanics is applied to the solar system, it shows that the
planets describe well-defined orbits around the sun. The gravitational force between the planets
is given by the expression G⋅m1m2r2G \cdot \frac{m_{1} m_{2}}{r^{2}}G⋅r2m1​m2​​, where
m1m_{1}m1​and m2m_{2}m2​are the masses, rrr is the distance of separation of the masses,
and GGG is the gravitational constant. The theory can also calculate precisely the planetary
orbits, and these are in agreement with the experimental measurements.

The similarity between the solar system and the nuclear model suggests that electrons should
move around the nucleus in well-defined orbits. Further, the Coulomb force kq1q2/r2k q_{1}
q_{2} / r^{2}kq1​q2​/r2, where q1q_{1}q1​and q2q_{2}q2​are the charges, rrr is the distance of
separation of the charges, and kkk is the proportionality constant) between the electron and the
nucleus is mathematically similar to the gravitational force. However, when a body is moving in
an orbit, it undergoes acceleration even if it is moving with a constant speed in an orbit because
of changing direction. So an electron in the nuclear model describing planet-like orbits is under
acceleration. According to the electromagnetic theory of Maxwell, charged particles when
accelerated should emit electromagnetic radiation. Therefore, an electron in an orbit will emit
radiation, the energy carried by radiation comes from electronic motion. The orbit will thus
continue to shrink. Calculations show that it should take an electron only 10−810^{-8}10−8 s to
spiral into the nucleus. But this does not happen. Thus, the Rutherford model cannot explain the
stability of an atom. If the motion of an electron is described on the basis of classical mechanics
and electromagnetic theory, one may ask that since the motion of electrons in orbits is leading to
the instability of the atom, then why not consider electrons as stationary around the nucleus. If
the electrons were stationary, electrostatic attraction between the dense nucleus and the
electrons would pull the electrons toward the nucleus to form a miniature version of Thomson's
model of the atom.

Another serious drawback of the Rutherford model is that it says nothing about the distribution
of the electrons around the nucleus and the energies of these electrons.

Developments Leading to Bohr's Model of Atom

Historically, results observed from the studies of interactions of radiations with matter have
provided immense information regarding the structure of atoms and molecules. Niels Bohr
utilized these results to improve upon the model proposed by Rutherford. Two developments
played a major role in the formulation of Bohr's model of the atom. These were:

1.​ Dual character of electromagnetic radiation, which means that radiations possess both
wave-like and particle-like properties.
2.​ Experimental results regarding atomic spectra.

Wave Nature of Electromagnetic Radiation

In the mid-nineteenth century, physicists actively studied the absorption and emission of
radiation by heated objects, called thermal radiations. They tried to find out what thermal
radiation is made of. It is now a well-known fact that thermal radiations consist of
electromagnetic waves of various frequencies or wavelengths. It is based on a number of
modern concepts, which were unknown in the mid-nineteenth century. The first active study of
thermal radiation laws occurred in the 1850s, and the theory of electromagnetic waves and the
emission of such waves by accelerating charged particles was developed in the early 1870s by
James Clerk Maxwell, which was experimentally confirmed later by Heinrich Hertz. Here, we will
learn some facts about electromagnetic radiations.

James Maxwell (1870) was the first to give a comprehensive explanation about the interaction
between charged bodies and the behavior of electrical and magnetic fields on a macroscopic
level. He suggested that when an electrically charged particle moves under acceleration,
alternating electrical and magnetic fields are produced and transmitted. These fields are
transmitted in the form of waves called electromagnetic waves or electromagnetic radiation.

Light is the form of radiation known from early days, and speculation about its nature dates back
to remote ancient times. In earlier days (Newton), light was supposed to be made of particles
(corpuscules). It was only in the 19th century that the wave nature of light was established.

Maxwell was again the first to reveal that light waves are associated with oscillating electric and
magnetic character.

Although electromagnetic wave motion is complex in nature, we will consider here only a few
simple properties:

1.​ The oscillating electric and magnetic fields produced by oscillating charged particles are
perpendicular to each other, and both are perpendicular to the direction of propagation of
the wave.
2.​ Unlike sound waves or waves produced in water, electromagnetic waves do not require
a medium and can move in a vacuum.
3.​ It is now well established that there are many types of electromagnetic radiations, which
differ from one another in wavelength (or frequency). These constitute what is called the
electromagnetic spectrum. Different regions of the spectrum are identified by different
names. Some examples are: radio frequency region around 10610^{6}106 Hz, used for
broadcasting; microwave region around 101010^{10}1010 Hz, used for radar; infrared
region around 101310^{13}1013 Hz, used for heating; ultraviolet region around
101610^{16}1016 Hz, a component of the sun's radiation. The small portion around
101510^{15}1015 Hz is what is ordinarily called visible light. It is only this part that our
eyes can see (or detect). Special instruments are required to detect non-visible radiation.
4.​ Different kinds of units are used to represent electromagnetic radiation. These radiations
are characterized by the properties, namely, frequency (v) and wavelength (λ). The SI
unit for frequency (v) is hertz (Hz, s^-1), after Heinrich Hertz. It is defined as the number
of waves that pass a given point in one second. Wavelength should have the units of
length, and as you know, the SI unit of length is meter (m). Since electromagnetic
radiation consists of different kinds of waves of much smaller wavelengths, smaller units
are used. The frequency (v), wavelength (λ), and velocity of light (c) are related by the
equation:

c=vλ c = v \lambdac=vλ

In a vacuum, all types of electromagnetic radiations, regardless of wavelength, travel at the

same speed, i.e., 3.0×1083.0 \times 10^{8}3.0×108 m s^-1 (2.997925 x 10^8 m s^-1, to be
precise). This is called the speed of light and is given the symbol 'c'. The other commonly used
quantity, especially in spectroscopy, is the wavenumber (v). It is defined as the number of
wavelengths per unit length. Its units are the reciprocal of the wavelength unit, i.e., m^-1.
However, the commonly used unit is cm^-1 (not an SI unit).
Particle Nature of Electromagnetic Radiation: Planck's Quantum Theory

Some of the experimental phenomena, such as diffraction and interference, can be explained by
the wave nature of electromagnetic radiation. However, the following are some observations
that could not be explained with the help of even the electromagnetic theory of 19th-century
physics (known as classical physics):

1.​ The nature of the emission of radiation from hot bodies (black-body radiation).
2.​ The ejection of electrons from a metal surface when radiation strikes it (photoelectric
effect).
3.​ The variation of heat capacity of solids as a function of temperature.
4.​ Line spectra of atoms with special reference to hydrogen.

These phenomena indicate that the system can take energy only in discrete amounts. All
possible energies cannot be taken up or radiated.

It is noteworthy that the first concrete explanation for the phenomenon of black-body radiation
mentioned above was given by Max Planck in 1900. Let us first try to understand this
phenomenon, which is given below:

Hot objects emit electromagnetic radiations over a wide range of wavelengths. At high
temperatures, an appreciable proportion of radiation is in the visible region of the spectrum. As
the temperature is raised, a higher proportion of short wavelength (blue light) is generated. For
example, when an iron rod is heated in a furnace, it first turns to dull red and then progressively
becomes more and more red as the temperature increases. As this is heated further, the
radiation emitted becomes white and then becomes blue as the temperature becomes very
high. This means that red radiation is most intense at a particular temperature, and the blue
radiation is more intense at another temperature. This means the intensities of radiations of
different wavelengths emitted by a hot body depend upon its temperature. By the late 1850s, it
was known that objects made of different materials and kept at different temperatures emit
different amounts of radiation. Also, when the surface of an object is irradiated with light
(electromagnetic radiation), a part of the radiant energy is generally reflected as such, a part is
absorbed, and a part of it is transmitted. The reason for incomplete absorption is that ordinary
objects are, as a rule, imperfect absorbers of radiation. An ideal body that emits and absorbs
radiations of all frequencies uniformly is called a black body, and the radiation emitted by such a
body is called black-body radiation. In practice, no such body exists. Carbon black approximates
fairly closely to a black body. A good physical approximation to a black body is a cavity with a
tiny hole, which has no other opening. Any ray entering the hole will be reflected by the cavity
walls and will eventually be absorbed by the walls. A black body is also a perfect radiator of
radiant energy. Furthermore, a black body is in thermal equilibrium with its surroundings. It
radiates the same amount of energy per unit area as it absorbs from its surroundings in any
given time. The amount of light emitted (intensity of radiation) from a black body and its spectral
distribution depends only on its temperature. At a given temperature, the intensity of radiation
emitted increases with the increase of wavelength, reaches a maximum value at a given
wavelength, and then starts decreasing with further increase of wavelength. Also, as the
temperature increases, the maxima of the curve shift to shorter wavelengths. Several attempts
were made to predict the intensity of radiation as a function of wavelength, but the results of the
above experiment could not be explained satisfactorily on the basis of the wave theory of light.
Max Planck arrived at a satisfactory relationship by making an assumption that absorption and
emission of radiation arise from oscillators, i.e., atoms in the wall of the black body. Their
frequency of oscillation is changed by interaction with oscillators of electromagnetic radiation.
Planck assumed that radiation could be subdivided into discrete chunks of energy. He
suggested that atoms and molecules could emit or absorb energy only in discrete quantities and
not in a continuous manner. He 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
quantum of radiation is proportional to its frequency (v) and is expressed by the equation:

E=hv E = h vE=hv

The proportionality constant, 'h', is known as Planck's constant and has the value
6.626×10−346.626 \times 10^{-34}6.626×10−34 J s.

With this theory, Planck was able to explain the distribution of intensity in the radiation from a
black body as a function of frequency or wavelength at different temperatures.

Quantization has been compared to standing on a staircase. A person can stand on any step of
a staircase, but it is not possible for them to stand between two steps. The energy can take any
one of the values from the following set, but cannot take on any values between them:

E=0,hv,2hv,3hv…nhv… E = 0, h v, 2 h v, 3 h v \ldots n h v \ldotsE=0,hv,2hv,3hv…nhv…

Photoelectric Effect

In 1887, H. Hertz performed a very interesting experiment in which electrons (or electric current)
were ejected when certain metals (for example, potassium, rubidium, cesium, etc.) were
exposed to a beam of light. The phenomenon is called the photoelectric effect. The results
observed in this experiment were:

1.​ The electrons are ejected from the metal surface as soon as the beam of light strikes the
surface, i.e., there is no time lag between the striking of the light beam and the ejection
of electrons from the metal surface.
2.​ The number of electrons ejected is proportional to the intensity or brightness of the light.
3.​ For each metal, there is a characteristic minimum frequency, v0v_{0}v0​(also known as
threshold frequency), below which the photoelectric effect is not observed. At a
frequency v>v0v > v_{0}v>v0​, the ejected electrons come out with a certain kinetic
energy. The kinetic energies of these electrons increase with the increase of frequency
of the light used.

All the above results could not be explained on the basis of the laws of classical physics.
According to the latter, the energy content of the beam of light depends upon the brightness of
the light. In other words, the number of electrons ejected and the kinetic energy associated with
them should depend on the brightness of the light. It has been observed that, although the
number of electrons ejected does depend upon the brightness of the light, the kinetic energy of
the ejected electrons does not. For example, red light (v=(4.3v = (4.3v=(4.3 to 4.6)×10144.6)
\times 10^{14}4.6)×1014 Hz) of any brightness (intensity) may shine on a piece of potassium
metal for hours, but no photoelectrons are ejected. But as soon as even a very weak yellow light
(v=5.1−5.2×1014v = 5.1-5.2 \times 10^{14}v=5.1−5.2×1014 Hz) shines on the potassium metal,
the photoelectric effect is observed. The threshold frequency (v0v_{0}v0​) for potassium metal is
5.0×10145.0 \times 10^{14}5.0×1014 Hz.

Einstein (1905) was able to explain the photoelectric effect using Planck's quantum theory of
electromagnetic radiation as a starting point.

Shining a beam of light onto a metal surface can, therefore, be viewed as shooting a beam of
particles, the photons. When a photon of sufficient energy strikes an electron in the atom of the
metal, it transfers its energy instantaneously to the electron during the collision, and the electron
is ejected without any time lag or delay. The greater the energy possessed by the photon, the
greater the transfer of energy to the electron, and the greater the kinetic energy of the ejected
electron. In other words, the kinetic energy of the ejected electron is proportional to the
frequency of the electromagnetic radiation. Since the striking photon has energy equal to hvh
vhv and the minimum energy required to eject the electron is hv0h v_{0}hv0​(also called work
function, W0W_{0}W0​), then the difference in energy (hv−hv0h v - h v_{0}hv−hv0​) is transferred
as the kinetic energy of the photoelectron. Following the conservation of energy principle, the
kinetic energy of the ejected electron is given by the equation:

hv=hv0+12mev2 h v = h v_{0} + \frac{1}{2} m_{e} v^{2}hv=hv0​+21​me​v2

where mem_{e}me​is the mass of the electron and vvv is the velocity associated with the
ejected electron. Lastly, a more intense beam of light consists of a larger number of photons;
consequently, the number of electrons ejected is also larger compared to that in an experiment
in which a beam of weaker intensity of light is employed.

Dual Behavior of Electromagnetic Radiation

The particle nature of light posed a dilemma for scientists. On the one hand, it could explain
black-body radiation and the photoelectric effect satisfactorily, but on the other hand, it was not
consistent with the known wave behavior of light, which could account for the phenomena of
interference and diffraction. The only way to resolve the dilemma was to accept the idea that
light possesses both particle and wave-like properties, i.e., light has dual behavior. Depending
on the experiment, we find that light behaves either as a wave or as a stream of particles.
Whenever radiation interacts with matter, it displays particle-like properties in contrast to the
wave-like properties (interference and diffraction), which it exhibits when it propagates. This
concept was totally alien to the way scientists thought about matter and radiation, and it took
them a long time to become convinced of its validity. It turns out, as you shall see later, that
some microscopic particles like electrons also exhibit this wave-particle duality.
Bohr's Model for Hydrogen Atom

Neils Bohr (1913) was the first to explain quantitatively the general features of the structure of
the hydrogen atom and its spectrum. He used Planck's concept of the quantization of energy.
Though the theory is not modern quantum mechanics, it can still be used to rationalize many
points in the atomic structure and spectra. Bohr's model for the hydrogen atom is based on the
following postulates:

1.​ The electron in the hydrogen atom can move around the nucleus in a circular path of
fixed radius and energy. These paths are called orbits, stationary states, or allowed
energy states. These orbits are arranged concentrically around the nucleus.
2.​ The energy of an electron in the orbit does not change with time. However, the electron
will move from a lower stationary state to a higher stationary state when the required
amount of energy is absorbed by the electron, or energy is emitted when the electron
moves from a higher stationary state to a lower stationary state. The energy change
does not take place in a continuous manner.
3.​ The frequency of radiation absorbed or emitted when transition occurs between two
stationary states that differ in energy by ΔE\Delta EΔE is given by:

v=ΔEh=E2−E1h v = \frac{\Delta E}{h} = \frac{E_{2} - E_{1}}{h}v=hΔE​=hE2​−E1​​

where E1E_{1}E1​and E2E_{2}E2​are the energies of the lower and higher allowed energy
states, respectively. This expression is commonly known as Bohr's frequency rule. 4. The
angular momentum of an electron is quantized. In a given stationary state, it can be expressed
as:

mevr=n⋅h2πn=1,2,3… m_{e} v r = n \cdot \frac{h}{2 \pi} \quad n = 1, 2, 3

\ldotsme​vr=n⋅2πh​n=1,2,3…

where mem_{e}me​is the mass of the electron, vvv is the velocity, and rrr is the radius of the
orbit in which the electron is moving.

Thus, an electron can move only in those orbits for which its angular momentum is an integral
multiple of h/2πh / 2 \pih/2π. That means angular momentum is quantized. Radiation is emitted
or absorbed only when the transition of the electron takes place from one quantized value of
angular momentum to another. Therefore, Maxwell's electromagnetic theory does not apply
here, which is why only certain fixed orbits are allowed.

According to Bohr's theory for the hydrogen atom:

1.​ The stationary states for the electron are numbered n=1,2,3…n = 1, 2, 3 \ldotsn=1,2,3….
These integral numbers are known as principal quantum numbers.
2.​ The radii of the stationary states are expressed as:

rn=n2a0 r_{n} = n^{2} a_{0}rn​=n2a0​

where a0=52.9a_{0} = 52.9a0​=52.9 pm. Thus, the radius of the first stationary state, called the
Bohr orbit, is 52.9 pm. Normally, the electron in the hydrogen atom is found in this orbit (i.e.,
n=1n = 1n=1). As nnn increases, the value of rrr will increase. In other words, the electron will
be present away from the nucleus. 3. The most important property associated with the electron
is the energy of its stationary state. It is given by the expression:

En=−RH(1n2)n=1,2,3… E_{n} = -R_{H} \left( \frac{1}{n^{2}} \right) \quad n = 1, 2, 3

\ldotsEn​=−RH​(n21​)n=1,2,3…

where RHR_{H}RH​is called the Rydberg constant and its value is 2.18×10−182.18 \times
10^{-18}2.18×10−18 J. The energy of the lowest state, also called the ground state, is
E1=−2.18×10−18(112)=−2.18×10−18E_{1} = -2.18 \times 10^{-18} \left( \frac{1}{1^{2}} \right) =
-2.18 \times 10^{-18}E1​=−2.18×10−18(121​)=−2.18×10−18 J. The energy of the stationary state
for n=2n = 2n=2 will be E2=−2.18×10−18E_{2} = -2.18 \times 10^{-18}E2​=−2.18×10−18 J
(122)=−0.545×10−18\left( \frac{1}{2^{2}} \right) = -0.545 \times 10^{-18}(221​)=−0.545×10−18 J.
4. It is also possible to calculate the velocities of electrons moving in these orbits. Although the
precise equation is not given here, qualitatively the magnitude of the velocity of the electron
increases with the increase of positive charge on the nucleus and decreases with the increase
of the principal quantum number.

Explanation of Line Spectrum of Hydrogen

The line spectrum observed in the case of the hydrogen atom, as mentioned in section 2.3.3,
can be explained quantitatively using Bohr's model. According to assumption 2, radiation
(energy) is absorbed if the electron moves from the orbit of a smaller principal quantum number
to the orbit of a higher principal quantum number, whereas the radiation (energy) is emitted if
the electron moves from a higher orbit to a lower orbit. The energy gap between the two orbits is
given by equation (2.16):

ΔE=Ef−Ei \Delta E = E_{f} - E_{i}ΔE=Ef​−Ei​

Combining equations (2.13) and (2.16):

ΔE=RH(1ni2−1nf2) \Delta E = R_{H} \left( \frac{1}{n_{i}^{2}} - \frac{1}{n_{f}^{2}}

\right)ΔE=RH​(ni2​1​−nf2​1​)

where nin_{i}ni​and nfn_{f}nf​stand for the initial orbit and final orbits.

The frequency (v) associated with the absorption and emission of the photon can be evaluated
by using the equation:

v=ΔEh=RHh(1ni2−1nf2) v = \frac{\Delta E}{h} = \frac{R_{H}}{h} \left( \frac{1}{n_{i}^{2}} -

\frac{1}{n_{f}^{2}} \right)v=hΔE​=hRH​​(ni2​1​−nf2​1​)

and in terms of wavenumbers (vˉ\bar{v}vˉ):

vˉ=vc=RHhc(1ni2−1nf2) \bar{v} = \frac{v}{c} = \frac{R_{H}}{h c} \left( \frac{1}{n_{i}^{2}} -
\frac{1}{n_{f}^{2}} \right)vˉ=cv​=hcRH​​(ni2​1​−nf2​1​)

In the case of the absorption spectrum, nf>nin_{f} > n_{i}nf​>ni​, and the term in the parenthesis is
positive, and energy is absorbed. On the other hand, in the case of the emission spectrum,
ni>nfn_{i} > n_{f}ni​>nf​, ΔE\Delta EΔE is negative, and energy is released.

The expression (2.17) is similar to that used by Rydberg (2.9), derived empirically using the
experimental data available at that time. Further, each spectral line, whether in the absorption or
emission spectrum, can be associated with a particular transition in the hydrogen atom. In the
case of a large number of hydrogen atoms, different possible transitions can be observed, thus
leading to a large number of spectral lines. The brightness or intensity of spectral lines depends
upon the number of photons of the same wavelength or frequency absorbed or emitted.

Limitations of Bohr's Model

Bohr's model of the hydrogen atom was no doubt an improvement over Rutherford's nuclear
model, as it could account for the stability and line spectra of the hydrogen atom and
hydrogen-like ions (for example, He+, Li2+, Be3+, etc.). However, Bohr's model was too simple
to account for the following points:

1.​ It fails to account for the finer details (doublet, i.e., two closely spaced lines) of the
hydrogen atom spectrum observed using sophisticated spectroscopic techniques. This
model is also unable to explain the spectrum of atoms other than hydrogen, for example,
the helium atom, which possesses only two electrons. Further, Bohr's theory was also
unable to explain the splitting of spectral lines in the presence of a magnetic field
(Zeeman effect) or an electric field (Stark effect).
2.​ It could not explain the ability of atoms to form molecules by chemical bonds.

In other words, taking into account the points mentioned above, one needs a better theory that
can explain the salient features of the structure of complex atoms.

Towards Quantum Mechanical Model of the Atom

In view of the shortcomings of Bohr's model, attempts were made to develop a more suitable
and general model for atoms. Two important developments that contributed significantly to the
formulation of such a model were:

1.​ Dual behavior of matter.

2.​ Heisenberg uncertainty principle.

Dual Behavior of Matter

The French physicist de Broglie, in 1924, proposed that matter, like radiation, should also exhibit
dual behavior, i.e., both particle and wave-like properties. This means that just as the photon
has momentum as well as wavelength, electrons should also have momentum as well as
wavelength. De Broglie, from this analogy, gave the following relation between wavelength (λ)
and momentum (p) of a material particle:

λ=hmv=hp \lambda = \frac{h}{m v} = \frac{h}{p}λ=mvh​=ph​

where mmm is the mass of the particle, vvv is its velocity, and ppp is its momentum. De
Broglie's prediction was confirmed experimentally when it was found that an electron beam
undergoes diffraction, a phenomenon characteristic of waves. This fact has been put to use in
making an electron microscope, which is based on the wave-like behavior of electrons, just as
an ordinary microscope utilizes the wave nature of light. An electron microscope is a powerful
tool in modern scientific research because it achieves a magnification of about 15 million times.

It needs to be noted that according to de Broglie, every object in motion has a wave character.
The wavelengths associated with ordinary objects are so short (because of their large masses)
that their wave properties cannot be detected. The wavelengths associated with electrons and
other subatomic particles (with very small mass) can, however, be detected experimentally.

Heisenberg's Uncertainty Principle

Werner Heisenberg, a German physicist, in 1927, stated the uncertainty principle, which is a
consequence of the dual behavior of matter and radiation. It states that it is impossible to
determine simultaneously the exact position and exact momentum (or velocity) of an electron.
Mathematically, it can be given as:

Δx×Δpx≥h4π \Delta x \times \Delta p_{x} \geq \frac{h}{4 \pi}Δx×Δpx​≥4πh​

or

Δx×Δ(mvx)≥h4π \Delta x \times \Delta (m v_{x}) \geq \frac{h}{4 \pi}Δx×Δ(mvx​)≥4πh​

or

Δx×Δvx≥h4πm \Delta x \times \Delta v_{x} \geq \frac{h}{4 \pi m}Δx×Δvx​≥4πmh​

where Δx\Delta xΔx is the uncertainty in position and Δpx\Delta p_{x}Δpx​(or Δvx\Delta
v_{x}Δvx​) is the uncertainty in momentum (or velocity) of the particle. If the position of the
electron is known with a high degree of accuracy (Δx\Delta xΔx is small), then the velocity of the
electron will be uncertain (Δ(vx)\Delta (v_{x})Δ(vx​) is large). On the other hand, if the velocity of
the electron is known precisely (Δ(vx)\Delta (v_{x})Δ(vx​) is small), then the position of the
electron will be uncertain (Δx\Delta xΔx will be large). Thus, if we carry out some physical
measurements on the electron's position or velocity, the outcome will always depict a fuzzy or
blur picture.

The uncertainty principle can be best understood with the help of an example. Suppose you are
asked to measure the thickness of a sheet of paper with an unmarked meter stick. Obviously,
the results obtained would be extremely inaccurate and meaningless. In order to obtain any
accuracy, you should use an instrument graduated in units smaller than the thickness of a sheet
of paper. Analogously, in order to determine the position of an electron, we must use a meter
stick calibrated in units smaller than the dimensions of an electron (keep in mind that an
electron is considered as a point charge and is therefore dimensionless). To observe an
electron, we can illuminate it with "light" or electromagnetic radiation. The "light" used must have
a wavelength smaller than the dimensions of an electron. The high momentum photons of such
light (p=hλp = \frac{h}{\lambda}p=λh​) would change the energy of electrons by collisions. In this
process, we would no doubt be able to calculate the position of the electron, but we would know
very little about the velocity of the electron after the collision.

Significance of Uncertainty Principle

One of the important implications of the Heisenberg Uncertainty Principle is that it rules out the
existence of definite paths or trajectories of electrons and other similar particles. The trajectory
of an object is determined by its location and velocity at various moments. If we know where a
body is at a particular instant and if we also know its velocity and the forces acting on it at that
instant, we can tell where the body would be sometime later. We therefore conclude that the
position of an object and its velocity fix its trajectory. Since for a sub-atomic object such as an
electron, it is not possible simultaneously to determine the position and velocity at any given
instant to an arbitrary degree of precision, it is not possible to talk of the trajectory of an
electron.

The effect of the Heisenberg Uncertainty Principle is significant only for the motion of
microscopic objects and is negligible for that of macroscopic objects. This can be seen from the
following examples.

If the uncertainty principle is applied to an object of mass, say about a milligram

(10−610^{-6}10−6 kg), then:

Δv⋅Δx=h4π⋅m=6.626×10−34 J s4×3.1416×10−6 kg≈10−28 m2 s−1 \Delta v \cdot \Delta x =

\frac{h}{4 \pi \cdot m} = \frac{6.626 \times 10^{-34} \, \text{J s}}{4 \times 3.1416 \times 10^{-6} \,
\text{kg}} \approx 10^{-28} \, \text{m}^2 \,
\text{s}^{-1}Δv⋅Δx=4π⋅mh​=4×3.1416×10−6kg6.626×10−34J s​≈10−28m2s−1

The value of ΔvΔx\Delta v \Delta xΔvΔx obtained is extremely small and is insignificant.
Therefore, one may say that in dealing with milligram-sized or heavier objects, the associated
uncertainties are hardly of any real consequence.

In the case of a microscopic object like an electron, on the other hand, Δv⋅Δx\Delta v \cdot
\Delta xΔv⋅Δx obtained is much larger, and such uncertainties are of real consequence. For
example, for an electron whose mass is 9.11×10−319.11 \times 10^{-31}9.11×10−31 kg,
according to the Heisenberg uncertainty principle:

Δv⋅Δx=h4πm=6.626×10−34 J s4×3.1416×9.11×10−31 kg=10−4 m2 s−1 \Delta v \cdot \Delta x =

\frac{h}{4 \pi m} = \frac{6.626 \times 10^{-34} \, \text{J s}}{4 \times 3.1416 \times 9.11 \times
10^{-31} \, \text{kg}} = 10^{-4} \, \text{m}^2 \,
\text{s}^{-1}Δv⋅Δx=4πmh​=4×3.1416×9.11×10−31kg6.626×10−34J s​=10−4m2s−1

It therefore means that if one tries to find the exact location of the electron, say to an uncertainty
of only 10−810^{-8}10−8 m, then the uncertainty Δv\Delta vΔv in velocity would be:

10−4 m2 s−110−8 m≈104 m s−1 \frac{10^{-4} \, \text{m}^2 \, \text{s}^{-1}}{10^{-8} \, \text{m}}

\approx 10^{4} \, \text{m s}^{-1}10−8m10−4m2s−1​≈104m s−1

which is so large that the classical picture of electrons moving in Bohr's orbits (fixed) cannot
hold good. It therefore means that the precise statements of the position and momentum of
electrons have to be replaced by the statements of probability that the electron has at a given
position and momentum. This is what happens in the quantum mechanical model of the atom.

Quantum Mechanical Model of Atom

Classical mechanics, based on Newton's laws of motion, successfully describes the motion of
all macroscopic objects such as a falling stone, orbiting planets, etc., which have essentially a
particle-like behavior as shown in the previous section. However, it fails when applied to
microscopic objects like electrons, atoms, molecules, etc. This is mainly because of the fact that
classical mechanics ignores the concept of dual behavior of matter, especially for sub-atomic
particles, and the uncertainty principle. The branch of science that takes into account this dual
behavior of matter is called quantum mechanics.

Quantum mechanics is a theoretical science that deals with the study of the motions of
microscopic objects that have both observable wave-like and particle-like properties. It specifies
the laws of motion that these objects obey. When quantum mechanics is applied to macroscopic
objects (for which wave-like properties are insignificant), the results are the same as those from
classical mechanics.

Quantum mechanics was developed independently in 1926 by Werner Heisenberg and Erwin
Schrödinger. Here, however, we shall be discussing the quantum mechanics that is based on
the ideas of wave motion. The fundamental equation of quantum mechanics was developed by
Schrödinger, and it won him the Nobel Prize in Physics in 1933. This equation, which
incorporates the wave-particle duality of matter as proposed by de Broglie, is quite complex,
and knowledge of higher mathematics is needed to solve it. You will learn its solutions for
different systems in higher classes.

For a system (such as an atom or a molecule whose energy does not change with time), the
Schrödinger equation is written as H^Ψ=EΨ\hat{H} \Psi = E \PsiH^Ψ=EΨ, where H^\hat{H}H^ is
a mathematical operator called the Hamiltonian. Schrödinger gave a recipe for constructing this
operator from the expression for the total energy of the system. The total energy of the system
takes into account the kinetic energies of all the sub-atomic particles (electrons, nuclei), the
attractive potential between the electrons and nuclei, and the repulsive potential among the
electrons and nuclei individually. The solution of this equation gives EEE and Ψ\PsiΨ.
Hydrogen Atom and the Schrödinger Equation

When the Schrödinger equation is solved for the hydrogen atom, the solution gives the possible
energy levels the electron can occupy and the corresponding wave function(s) (Ψ\PsiΨ) of the
electron associated with each energy level. These quantized energy states and corresponding
wave functions, which are characterized by a set of three quantum numbers (principal quantum
number nnn, azimuthal quantum number lll, and magnetic quantum number mlm_{l}ml​), arise as
a natural consequence in the solution of the Schrödinger equation. When an electron is in any
energy state, the wave function corresponding to that energy state contains all information
about the electron. The wave function is a mathematical function whose value depends upon
the coordinates of the electron in the atom and does not carry any physical meaning. Such
wave functions of hydrogen or hydrogen-like species with one electron are called atomic
orbitals. Such wave functions pertaining to one-electron species are called one-electron
systems. The probability of finding an electron at a point within an atom is proportional to
∣Ψ∣2|\Psi|^{2}∣Ψ∣2 at that point. The quantum mechanical results of the hydrogen atom
successfully predict all aspects of the hydrogen atom spectrum, including some phenomena that
could not be explained by the Bohr model.

The application of the Schrödinger equation to multi-electron atoms presents a difficulty: the
Schrödinger equation cannot be solved exactly for a multi-electron atom. This difficulty can be
overcome by using approximate methods. Such calculations, with the aid of modern computers,
show that orbitals in atoms other than hydrogen do not differ in any radical way from the
hydrogen orbitals discussed above. The principal difference lies in the consequence of
increased nuclear charge. Because of this, all the orbitals are somewhat contracted. Further, as
you shall see later, unlike orbitals of hydrogen or hydrogen-like species, whose energies depend
only on the quantum number nnn, the energies of the orbitals in multi-electron atoms depend on
the quantum numbers nnn and lll.

Important Features of the Quantum Mechanical Model of Atom

The quantum mechanical model of the atom is the picture of the structure of the atom that
emerges from the application of the Schrödinger equation to atoms. The following are the
important features of the quantum mechanical model of the atom:

1.​ The energy of electrons in atoms is quantized (i.e., can only have certain specific
values), for example, when electrons are bound to the nucleus in atoms.
2.​ The existence of quantized electronic energy levels is a direct result of the wave-like
properties of electrons and are allowed solutions of the Schrödinger wave equation.
3.​ Both the exact position and exact velocity of an electron in an atom cannot be
determined simultaneously (Heisenberg uncertainty principle). The path of an electron in
an atom therefore cannot ever be determined or known accurately. That is why, as you
shall see later on, one talks of only the probability of finding the electron at different
points in an atom.
4.​ An atomic orbital is the wave function Ψ\PsiΨ for an electron in an atom. Whenever an
electron is described by a wave function, we say that the electron occupies that orbital.
 Since many such wave functions are possible for an electron, there are many atomic
orbitals in an atom. These "one-electron orbital wave functions" or orbitals form the basis
of the electronic structure of atoms. In each orbital, the electron has a definite energy. An
orbital cannot contain more than two electrons. In a multi-electron atom, the electrons
are filled in various orbitals in the order of increasing energy. For each electron of a
multi-electron atom, there shall therefore be an orbital wave function characteristic of the
orbital it occupies. All the information about the electron in an atom is stored in its orbital
wave function Ψ\PsiΨ, and quantum mechanics makes it possible to extract this
information out of Ψ\PsiΨ.
5.​ The probability of finding an electron at a point within an atom is proportional to the
square of the orbital wave function, i.e., ∣Ψ∣2|\Psi|^{2}∣Ψ∣2 at that point.
∣Ψ∣2|\Psi|^{2}∣Ψ∣2 is known as the probability density and is always positive. From the
value of ∣Ψ∣2|\Psi|^{2}∣Ψ∣2 at different points within an atom, it is possible to predict the
region around the nucleus where the electron will most probably be found.

Orbitals and Quantum Numbers

A large number of orbitals are possible in an atom. Qualitatively, these orbitals can be
distinguished by their size, shape, and orientation. An orbital of smaller size means there is
more chance of finding the electron near the nucleus. Similarly, shape and orientation mean that
there is more probability of finding the electron along certain directions than along others.
Atomic orbitals are precisely distinguished by what are known as quantum numbers. Each
orbital is designated by three quantum numbers labeled as n,ln, ln,l, and mlm_{l}ml​.

The principal quantum number 'n' is a positive integer with a value of n=1,2,3…n = 1, 2, 3
\ldotsn=1,2,3…. The principal quantum number determines the size and, to a large extent, the
energy of the orbital. For the hydrogen atom and hydrogen-like species (He+, Li2+, etc.), the
energy and size of the orbital depend only on 'n'.

The principal quantum number also identifies the shell. With the increase in the value of 'n', the
number of allowed orbitals increases and is given by 'n^2'. All the orbitals of a given value of 'n'
constitute a single shell of the atom and are represented by the following letters:

n=1234 n = 1 \quad 2 \quad 3 \quad 4n=1234

Shell = K L M N

The size of an orbital increases with the increase of the principal quantum number 'n'. In other
words, the electron will be located away from the nucleus. Since energy is required in shifting
away the negatively charged electron from the positively charged nucleus, the energy of the
orbital will increase with the increase of n.

The azimuthal quantum number 'l' is also known as the orbital angular momentum or subsidiary
quantum number. It defines the three-dimensional shape of the orbital. For a given value of n, l
can have n values ranging from 0 to n-1, that is, for a given value of n, the possible values of l
are: l=0,1,2,…(n−1)l = 0, 1, 2, \ldots (n-1)l=0,1,2,…(n−1).
For example, when n=1n = 1n=1, the value of l is only 0. For n=2n = 2n=2, the possible values
of l can be 0 and 1. For n=3n = 3n=3, the possible l values are 0, 1, and 2.

Each shell consists of one or more subshells or sub-levels. The number of subshells in a
principal shell is equal to the value of n. For example, in the first shell (n=1n = 1n=1), there is
only one subshell which corresponds to l=0l = 0l=0. There are two subshells (l=0,1l = 0, 1l=0,1)
in the second shell (n=2n = 2n=2), three (l=0,1,2l = 0, 1, 2l=0,1,2) in the third shell (n=3n =
3n=3), and so on. Each subshell is assigned an azimuthal quantum number (l). Subshells
corresponding to different values of l are represented by the following symbols:

Value for l=012345l = 0 \quad 1 \quad 2 \quad 3 \quad 4 \quad 5l=012345

Notation for subshell = s p d f g h

The magnetic orbital quantum number 'm_l' gives information about the spatial orientation of the
orbital with respect to a standard set of coordinate axes. For any subshell (defined by 'l' value),
2l+12l + 12l+1 values of mlm_{l}ml​are possible, and these values are given by:

ml=−l,−(l−1),−(l−2)…0,1…(l−2),(l−1),l m_{l} = -l, -(l-1), -(l-2) \ldots 0, 1 \ldots (l-2), (l-1),

lml​=−l,−(l−1),−(l−2)…0,1…(l−2),(l−1),l

Thus, for l=0l = 0l=0, the only permitted value of ml=0m_{l} = 0ml​=0 [2(0) + 1 = 1, one s orbital].
For l=1l = 1l=1, mlm_{l}ml​can be -1, 0, and +1 [2(1) + 1 = 3, three p orbitals]. For l=2l = 2l=2,
ml=−2,−1,0,+1m_{l} = -2, -1, 0, +1ml​=−2,−1,0,+1, and +2 [2(2) + 1 = 5, five d orbitals]. It should
be noted that the values of mlm_{l}ml​are derived from l and that the values of l are derived from
n.

Each orbital in an atom is therefore defined by a set of values for n,ln, ln,l, and mlm_{l}ml​. An
orbital described by the quantum numbers n=2,l=1,ml=0n = 2, l = 1, m_{l} = 0n=2,l=1,ml​=0 is an
orbital in the p subshell of the second shell. The following chart gives the relation between the
subshell and the number of orbitals associated with it:

Value of l=012345l = 0 \quad 1 \quad 2 \quad 3 \quad 4 \quad 5l=012345

Subshell notation = s p d f g h

Number of orbitals = 1 3 5 7 9 11

Electron spin 's': The three quantum numbers labeling an atomic orbital can be used equally
well to define its energy, shape, and orientation. But all these quantum numbers are not enough
to explain the line spectra observed in the case of multi-electron atoms, i.e., some of the lines
actually occur in doublets (two lines closely spaced), triplets (three lines closely spaced), etc.
This suggests the presence of a few more energy levels than predicted by the three quantum
numbers.
In 1925, George Uhlenbeck and Samuel Goudsmit proposed the presence of the fourth
quantum number known as the electron spin quantum number (msm_{s}ms​). An electron spins
around its own axis, much in a similar way as the Earth spins around its own axis while
revolving around the sun. In other words, an electron has, besides charge and mass, intrinsic
spin angular momentum. The spin angular momentum of the electron—a vector quantity—can
have two orientations relative to the chosen axis. These two orientations are distinguished by
the spin quantum numbers msm_{s}ms​, which can take the values of +1/2 or -1/2. These are
called the two spin states of the electron and are normally represented by two arrows, ↑ (spin
up) and ↓ (spin down). Two electrons that have different msm_{s}ms​values (one +1/2 and the
other -1/2) are said to have opposite spins. An orbital cannot hold more than two electrons, and
these two electrons should have opposite spins.

To sum up, the four quantum numbers provide the following information:

1.​ 'n' defines the shell, determines the size of the orbital, and also, to a large extent, the
energy of the orbital.
2.​ There are n subshells in the nth shell. 'l' identifies the subshell and determines the shape
of the orbital. There are (2l + 1) orbitals of each type in a subshell, that is, one s orbital (l
= 0), three p orbitals (l = 1), and five d orbitals (l = 2) per subshell. To some extent, 'l'
also determines the energy of the orbital in a multi-electron atom.
3.​ 'm_l' designates the orientation of the orbital. For a given value of l, m_l has (2l + 1)
values, the same as the number of orbitals per subshell. It means that the number of
orbitals is equal to the number of ways in which they are oriented.
4.​ 'm_s' refers to the orientation of the spin of the electron.

Shapes of Atomic Orbitals

The orbital wave function or Ψ\PsiΨ for an electron in an atom has no physical meaning. It is
simply a mathematical function of the coordinates of the electron. However, for different orbitals,
the plots of the corresponding wave functions as a function of r (the distance from the nucleus)
are different. The variation of Ψ2\Psi^{2}Ψ2 as a function of r for 1s and 2s orbitals is given in
Fig. 2.12(b). Here again, you may note that the curves for 1s and 2s orbitals are different.

It may be noted that for the 1s orbital, the probability density is maximum at the nucleus and it
decreases sharply as we move away from it. On the other hand, for the 2s orbital, the probability
density first decreases sharply to zero and again starts increasing. After reaching a small
maxima, it decreases again and approaches zero as the value of r increases further. The region
where this probability density function reduces to zero is called nodal surfaces or simply nodes.
In general, it has been found that the ns orbital has (n-1) nodes, that is, the number of nodes
increases with the increase of the principal quantum number n. In other words, the number of
nodes for the 2s orbital is one, two for the 3s, and so on.

These probability density variations can be visualized in terms of charge cloud diagrams. In
these diagrams, the density of the dots in a region represents the electron probability density in
that region.
Boundary surface diagrams of constant probability density for different orbitals give a fairly good
representation of the shapes of the orbitals. In this representation, a boundary surface or
contour surface is drawn in space for an orbital on which the value of probability density
∣Ψ∣2|\Psi|^{2}∣Ψ∣2 is constant. In principle, many such boundary surfaces may be possible.
However, for a given orbital, only that boundary surface diagram of constant probability density
is taken to be a good representation of the shape of the orbital which encloses a region or
volume in which the probability of finding the electron is very high, say, 90%. The boundary
surface diagram for 1s and 2s orbitals is given in Fig. 2.13(b). One may ask a question: Why do
we not draw a boundary surface diagram that bounds a region in which the probability of finding
the electron is 100%? The answer to this question is that the probability density
∣Ψ∣2|\Psi|^{2}∣Ψ∣2 has always some value, however small it may be, at any finite distance from
the nucleus. It is therefore not possible to draw a boundary surface diagram of a rigid size in
which the probability of finding the electron is 100%. The boundary surface diagram for an s
orbital is actually a sphere centered on the nucleus. In two dimensions, this sphere looks like a
circle. It encloses a region in which the probability of finding the electron is about 90%.

Thus, we see that 1s and 2s orbitals are spherical in shape. In reality, all the s orbitals are
spherically symmetric, that is, the probability of finding the electron at a given distance is equal
in all directions. It is also observed that the size of the s orbital increases with the increase in n,
that is, 4s > 3s > 2s > 1s, and the electron is located further away from the nucleus as the
principal quantum number increases.

Boundary surface diagrams for three 2p orbitals (l = 1) are shown in Fig. 2.14. In these
diagrams, the nucleus is at the origin. Here, unlike s orbitals, the boundary surface diagrams are
not spherical. Instead, each p orbital consists of two sections called lobes that are on either side
of the plane that passes through the nucleus. The probability density function is zero on the
plane where the two lobes touch each other. The size, shape, and energy of the three orbitals
are identical. They differ, however, in the way the lobes are oriented. Since the lobes may be
considered to lie along the x, y, or z axis, they are given the designations 2p_x, 2p_y, and 2p_z.
It should be understood, however, that there is no simple relation between the values of m_l (-1,
0, and +1) and the x, y, and z directions. For our purpose, it is sufficient to remember that
because there are three possible values of m_l, there are therefore three p orbitals whose axes
are mutually perpendicular. Like s orbitals, p orbitals increase in size and energy with the
increase in the principal quantum number, and hence the order of the energy and size of various
p orbitals is 4p > 3p > 2p. Further, like s orbitals, the probability density functions for p orbitals
also pass through a value of zero, besides at zero and infinite distance, as the distance from the
nucleus increases. The number of nodes is given by (n-2), that is, the number of radial nodes is
1 for the 3p orbital, two for the 4p orbital, and so on.

For l = 2, the orbital is known as the d orbital, and the minimum value of the principal quantum
number (n) has to be 3, as the value of l cannot be greater than n-1. There are five m_l values
(-2, -1, 0, +1, and +2) for l = 2, and thus there are five d orbitals. The boundary surface diagram
of d orbitals is shown in Fig. 2.15.
The five d orbitals are designated as d_xy, d_yz, d_zx, d_x^2-y^2, and d_z^2. The shapes of the
first four d orbitals are similar to each other, whereas that of the fifth one, d_z^2, is different from
the others, but all five 3d orbitals are equivalent in energy. The d orbitals for which n is greater
than 3 (4d, 5d, etc.) also have shapes similar to the 3d orbital but differ in energy and size.

Besides the radial nodes (i.e., probability density function is zero), the probability density
functions for the np and nd orbitals are zero at the plane(s) passing through the nucleus (origin).
For example, in the case of the p_x orbital, the xy plane is a nodal plane; in the case of the d_yz
orbital, there are two nodal planes passing through the origin and bisecting the xy plane
containing the z-axis. These are called angular nodes, and the number of angular nodes is
given by 'l', i.e., one angular node for p orbitals, two angular nodes for 'd' orbitals, and so on.
The total number of nodes is given by (n-1), i.e., the sum of l angular nodes and (n-l-1) radial
nodes.

Energies of Orbitals

The energy of an electron in a hydrogen atom is determined solely by the principal quantum
number. Thus, the energy of the orbitals in a hydrogen atom increases as follows:

1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f < ...

and is depicted in Fig. 2.16. Although the shapes of 2s and 2p orbitals are different, an electron
has the same energy when it is in the 2s orbital as when it is present in the 2p orbital. The
orbitals having the same energy are called degenerate. The 1s orbital in a hydrogen atom, as
said earlier, corresponds to the most stable condition and is called the ground state, and an
electron residing in this orbital is most strongly held by the nucleus. An electron in the 2s, 2p, or
higher orbitals in a hydrogen atom is in an excited state.

The energy of an electron in a multi-electron atom, unlike that of the hydrogen atom, depends
not only on its principal quantum number (shell) but also on its azimuthal quantum number
(subshell). That is, for a given principal quantum number, s, p, d, f, etc., all have different
energies. Within a given principal quantum number, the energy of orbitals increases in the order
s < p < d < f. For higher energy levels, these differences are sufficiently pronounced, and
staggering of orbital energy may result, e.g., 4s < 3d and 6s < 5d; 4f < 6p. The main reason for
having different energies of the subshells is the mutual repulsion among the electrons in
multi-electron atoms. The only electrical interaction present in the hydrogen atom is the
attraction between the negatively charged electron and the positively charged nucleus. In
multi-electron atoms, besides the presence of attraction between the electron and nucleus,
there are repulsion terms between every electron and other electrons present in the atom. Thus,
the stability of an electron in a multi-electron atom is because the total attractive interactions are
more than the repulsive interactions. In general, the repulsive interaction of the electrons in the
outer shell with the electrons in the inner shell is more important. On the other hand, the
attractive interactions of an electron increase with the increase of positive charge (Ze) on the
nucleus. Due to the presence of electrons in the inner shells, the electron in the outer shell will
not experience the full positive charge of the nucleus (Ze). The effect will be lowered due to the
partial screening of the positive charge on the nucleus by the inner shell electrons. This is
known as the shielding of the outer shell electrons from the nucleus by the inner shell electrons,
and the net positive charge experienced by the outer electrons is known as the effective nuclear
charge (Z_eff e). Despite the shielding of the outer electrons from the nucleus by the inner shell
electrons, the attractive force experienced by the outer shell electrons increases with the
increase of nuclear charge. In other words, the energy of interaction between the nucleus and
electron (that is, orbital energy) decreases (that is, more negative) with the increase of atomic
number (Z).

Both the attractive and repulsive interactions depend upon the shell and shape of the orbital in
which the electron is present. For example, electrons present in the spherical-shaped s orbital
shield the outer electrons from the nucleus more effectively compared to electrons present in
the p orbital. Similarly, electrons present in p orbitals shield the outer electrons from the nucleus
more than the electrons present in d orbitals, even though all these orbitals are present in the
same shell. Further, within a shell, due to the spherical shape of the s orbital, the s orbital
electron spends more time close to the nucleus compared to the p orbital electron, which
spends more time in the vicinity of the nucleus compared to the d orbital electron. In other
words, for a given shell (principal quantum number), the Z_eff experienced by the electron
decreases with the increase of the azimuthal quantum number (l), that is, the s orbital electron
will be more tightly bound to the nucleus than the p orbital electron, which in turn will be better
tightly bound than the d orbital electron. The energy of electrons in the s orbital will be lower
(more negative) than that of the p orbital electron, which will have less energy than that of the d
orbital electron, and so on. Since the extent of shielding from the nucleus is different for
electrons in different orbitals, it leads to the splitting of energy levels within the same shell (or
same principal quantum number), that is, the energy of the electron in an orbital, as mentioned
earlier, depends upon the values of n and l. Mathematically, the dependence of the energies of
the orbitals on n and l is quite complicated, but one simple rule is that the lower the value of (n +
l) for an orbital, the lower is its energy. If two orbitals have the same value of (n + l), the orbital
with the lower value of n will have the lower energy. Table 2.5 illustrates the (n + l) rule, and Fig.
2.16 depicts the energy levels of multi-electron atoms. It may be noted that different subshells of
a particular shell have different energies in the case of multi-electron atoms. However, in the
hydrogen atom, these have the same energy.

Filling of Orbitals in Atom

The distribution of electrons into the orbitals of different atoms takes place according to the
Aufbau principle, which is based on Pauli's exclusion principle, Hund's rule of maximum
multiplicity, and the relative energies of the orbitals.

Aufbau Principle

The word 'Aufbau' in German means 'building up.' The building up of orbitals means the filling
up of orbitals with electrons. The principle states: In the ground state of the atoms, the orbitals
are filled in the order of their increasing energies. In other words, electrons first occupy the
lowest energy orbital available to them and enter into higher energy orbitals only after the lower
energy orbitals are filled. As you have learned above, the energy of a given orbital depends
upon the effective nuclear charge, and different types of orbitals are affected to different extents.
Thus, there is no single ordering of energies of orbitals that will be universally correct for all
atoms.

However, the following order of energies of the orbitals is extremely useful:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, ...

The order may be remembered by using the method given in Fig. 2.17. Starting from the top,
the direction of the arrows gives the order of filling of orbitals, that is, starting from the right top
to the bottom left. With respect to the placement of outermost valence electrons, it is remarkably
accurate for all atoms. For example, the valence electron in potassium must choose between
the 3d and 4s orbitals, and as predicted by this sequence, it is found in the 4s orbital. The above
order should be assumed to be a rough guide to the filling of energy levels. In many cases, the
orbitals are similar in energy, and small changes in atomic structure may bring about a change
in the order of filling. Even then, the above series is a useful guide to the building of the
electronic structure of an atom, provided that it is remembered that exceptions may occur.

Pauli Exclusion Principle

The number of electrons to be filled in various orbitals is restricted by the exclusion principle,
given by the Austrian scientist Wolfgang Pauli (1926). According to this principle: No two
electrons in an atom can have the same set of four quantum numbers. The Pauli exclusion
principle can also be stated as: "Only two electrons may exist in the same orbital, and these
electrons must have opposite spin." This means that the two electrons can have the same value
of three quantum numbers n, l, and m_l but must have the opposite spin quantum number. The
restriction imposed by Pauli's exclusion principle on the number of electrons in an orbital helps
in calculating the capacity of electrons to be present in any subshell. For example, the subshell
1s comprises one orbital, and thus the maximum number of electrons present in the 1s subshell
can be two; in p and d subshells, the maximum number of electrons can be 6 and 10, and so
on. This can be summed up as: the maximum number of electrons in the shell with the principal
quantum number n is equal to 2n^2.

Hund's Rule of Maximum Multiplicity

This rule deals with the filling of electrons into the orbitals belonging to the same subshell (that
is, orbitals of equal energy, called degenerate orbitals). It states: Pairing of electrons in the
orbitals belonging to the same subshell (p, d, or f) does not take place until each orbital
belonging to that subshell has got one electron each, i.e., it is singly occupied.

Since there are three p, five d, and seven f orbitals, therefore, the pairing of electrons will start in
the p, d, and f orbitals with the entry of the 4th, 6th, and 8th electron, respectively. It has been
observed that half-filled and fully filled degenerate sets of orbitals acquire extra stability due to
their symmetry.
Electronic Configuration of Atoms

The distribution of electrons into the orbitals of different atoms is called its electronic
configuration. If one keeps in mind the basic rules that govern the filling of different atomic
orbitals, the electronic configurations of different atoms can be written very easily.

The electronic configuration of different atoms can be represented in two ways. For example:

1.​ snpbdc…s^{n} p^{b} d^{c} \ldotssnpbdc… notation

2.​ Orbital diagram

In the first notation, the subshell is represented by the respective letter symbol, and the number
of electrons present in the subshell is depicted as the superscript, like a, b, c, etc. The similar
subshell represented for different shells is differentiated by writing the principal quantum number
before the respective subshell. In the second notation, each orbital of the subshell is
represented by a box, and the electron is represented by an arrow (↑) a positive spin or an
arrow (↓) a negative spin. The advantage of the second notation over the first is that it
represents all four quantum numbers.

The hydrogen atom has only one electron, which goes into the orbital with the lowest energy,
namely 1s. The electronic configuration of the hydrogen atom is 1s^1, meaning that it has one
electron in the 1s orbital. The second electron in helium (He) can also occupy the 1s orbital. Its
configuration is therefore 1s^2. As mentioned above, the two electrons differ from each other
with opposite spin, as can be seen from the orbital diagram.

The third electron of lithium (Li) is not allowed in the 1s orbital because of the Pauli exclusion
principle. It therefore takes the next available choice, namely the 2s orbital. The electronic
configuration of Li is 1s^2 2s^1. The 2s orbital can accommodate one more electron. The
configuration of the beryllium (Be) atom is therefore 1s^2 2s^2.

In the next six elements—boron (B, 1s^2 2s^2 2p^1), carbon (C, 1s^2 2s^2 2p^2), nitrogen (N,
1s^2 2s^2 2p^3), oxygen (O, 1s^2 2s^2 2p^4), fluorine (F, 1s^2 2s^2 2p^5), and neon (Ne, 1s^2
2s^2 2p^6)—the 2p orbitals get progressively filled. This process is completed with the neon
atom. The orbital picture of these elements can be represented as follows:

The electronic configuration of the elements sodium (Na, 1s^2 2s^2 2p^6 3s^1) to argon (Ar,
1s^2 2s^2 2p^6 3s^2 3p^6) follows exactly the same pattern as the elements from lithium to
neon, with the difference that the 3s and 3p orbitals are getting filled now. This process can be
simplified if we represent the total number of electrons in the first two shells by the name of the
element neon (Ne). The electronic configuration of the elements from sodium to argon can be
written as (Na, [Ne] 3s^1) to (Ar, [Ne] 3s^2 3p^6). The electrons in the completely filled shells
are known as core electrons, and the electrons that are added to the electronic shell with the
highest principal quantum number are called valence electrons. For example, the electrons in
Ne are the core electrons, and the electrons from Na to Ar are the valence electrons. In
potassium (K) and calcium (Ca), the 4s orbital, being lower in energy than the 3d orbitals, is
occupied by one and two electrons, respectively.
A new pattern is followed beginning with scandium (Sc). The 3d orbital, being lower in energy
than the 4p orbital, is filled first. Consequently, in the next ten elements, scandium (Sc), titanium
(Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper
(Cu), and zinc (Zn), the five 3d orbitals are progressively occupied. We may be puzzled by the
fact that chromium and copper have five and ten electrons in 3d orbitals rather than four and
nine as their position would have indicated with two electrons in the 4s orbital. The reason is
that fully filled orbitals and half-filled orbitals have extra stability (that is, lower energy). Thus,
p^3, p^6, d^5, d^10, f^7, f^14, etc., configurations, which are either half-filled or fully filled, are
more stable. Chromium and copper therefore adopt the d^5 and d^10 configuration.

With the saturation of the 3d orbitals, the filling of the 4p orbital starts at gallium (Ga) and is
complete at krypton (Kr). In the next eighteen elements from rubidium (Rb) to xenon (Xe), the
pattern of filling the 5s, 4d, and 5p orbitals is similar to that of 4s, 3d, and 4p orbitals as
discussed above. Then comes the turn of the 6s orbital. In cesium (Cs) and barium (Ba), this
orbital contains one and two electrons, respectively. Then from lanthanum (La) to mercury (Hg),
the filling up of electrons takes place in 4f and 5d orbitals.

After this, the filling of 6p, then 7s, and finally 5f and 6d orbitals takes place. The elements after
uranium (U) are all short-lived and are all produced artificially. The electronic configurations of
the known elements (as determined by spectroscopic methods) are tabulated in Table 2.6.

One may ask what is the utility of knowing the electron configuration? The modern approach to
chemistry, in fact, depends almost entirely on electronic distribution to understand and explain
chemical behavior. For example, questions like why two or more atoms combine to form
molecules, why some elements are metals while others are nonmetals, why elements like
helium and argon are not reactive but elements like the halogens are reactive, find simple
explanations from the electronic configuration. These questions have no answer in the
Daltonian model of the atom. A detailed understanding of the electronic structure of the atom is
therefore very essential for getting an insight into the various aspects of modern chemical
knowledge.

Stability of Completely Filled and Half-Filled Subshells

The ground state electronic configuration of the atom of an element always corresponds to the
state of the lowest total electronic energy. The electronic configurations of most of the atoms
follow the basic rules given in Section 2.6.5. However, in certain elements such as Cu or Cr,
where the two subshells (4s and 3d) differ slightly in their energies, an electron shifts from a
subshell of lower energy (4s) to a subshell of higher energy (3d), provided such a shift results in
all orbitals of the subshell of higher energy getting either completely filled or half-filled. The
valence electronic configurations of Cr and Cu are therefore 3d^5 4s^1 and 3d^10 4s^1,
respectively, and not 3d^4 4s^2 and 3d^9 4s^2. It has been found that there is extra stability
associated with these electronic configurations.

Causes of Stability of Completely Filled and Half-Filled Subshells

The completely filled and completely half-filled subshells are stable due to the following reasons:

1.​ Symmetrical distribution of electrons: It is well known that symmetry leads to stability.
The completely filled or half-filled subshells have a symmetrical distribution of electrons
in them and are therefore more stable. Electrons in the same subshell (here 3d) have
equal energy but different spatial distributions. Consequently, their shielding of one
another is relatively small, and the electrons are more strongly attracted by the nucleus.
2.​ Exchange energy: The stabilizing effect arises whenever two or more electrons with the
same spin are present in the degenerate orbitals of a subshell. These electrons tend to
exchange their positions, and the energy released due to this exchange is called
exchange energy. The number of exchanges that can take place is maximum when the
subshell is either half-filled or completely filled. As a result, the exchange energy is
maximum, and so is the stability.

You may note that the exchange energy is at the basis of Hund's rule that electrons that enter
orbitals of equal energy have parallel spins as far as possible. In other words, the extra stability
of half-filled and completely filled subshells is due to: (i) relatively small shielding, (ii) smaller
Coulombic repulsion energy, and (iii) larger exchange energy. Details about the exchange
energy will be dealt with in higher classes.

Summary

Atoms are the building blocks of elements. They are the smallest parts of an element that
chemically react. The first atomic theory, proposed by John Dalton in 1808, regarded the atom
as the ultimate indivisible particle of matter. Towards the end of the nineteenth century, it was
proved experimentally that atoms are divisible and consist of three fundamental particles:
electrons, protons, and neutrons. The discovery of sub-atomic particles led to the proposal of
various atomic models to explain the structure of the atom.

Thomson, in 1898, proposed that an atom consists of a uniform sphere of positive electricity
with electrons embedded into it. This model, in which the mass of the atom is considered to be
evenly spread over the atom, was proved wrong by Rutherford's famous alpha-particle
scattering experiment in 1909. Rutherford concluded that an atom is made of a tiny positively
charged nucleus at its center, with electrons revolving around it in circular orbits. Rutherford's
model, which resembles the solar system, was no doubt an improvement over Thomson's
model, but it could not account for the stability of the atom, i.e., why the electron does not fall
into the nucleus. Further, it was also silent about the electronic structure of atoms, i.e., about the
distribution and relative energies of electrons around the nucleus. The difficulties of the
Rutherford model were overcome by Niels Bohr in 1913 in his model of the hydrogen atom.
Bohr postulated that the electron moves around the nucleus in circular orbits. Only certain orbits
can exist, and each orbit corresponds to a specific energy. Bohr calculated the energy of the
electron in various orbits and, for each orbit, predicted the distance between the electron and
nucleus. Bohr's model, though offering a satisfactory model for explaining the spectra of the
hydrogen atom, could not explain the spectra of multi-electron atoms. The reason for this was
soon discovered. In Bohr's model, an electron is regarded as a charged particle moving in a
well-defined circular orbit about the nucleus. The wave character of the electron is ignored in
Bohr's theory. An orbit is a clearly defined path, and this path can completely be defined only if
both the exact position and the exact velocity of the electron at the same time are known. This is
not possible according to the Heisenberg uncertainty principle. Bohr's model of the hydrogen
atom therefore not only ignores the dual behavior of the electron but also contradicts the
Heisenberg uncertainty principle.

Erwin Schrödinger, in 1926, proposed an equation called the Schrödinger equation to describe
the electron distributions in space and the allowed energy levels in atoms. This equation
incorporates de Broglie's concept of wave-particle duality and is consistent with the Heisenberg
uncertainty principle. When the Schrödinger equation is solved for the electron in a hydrogen
atom, the solution gives the possible energy states the electron can occupy and the
corresponding wave function(s) (Ψ\PsiΨ) of the electron associated with each energy state.
These quantized energy states and corresponding wave functions, which are characterized by a
set of three quantum numbers (principal quantum number n, azimuthal quantum number l, and
magnetic quantum number m_l), arise as a natural consequence in the solution of the
Schrödinger equation. The restrictions on the values of these three quantum numbers also
come naturally from this solution. The quantum mechanical model of the hydrogen atom
successfully predicts all aspects of the hydrogen atom spectrum, including some phenomena
that could not be explained by the Bohr model.

According to the quantum mechanical model of the atom, the electron distribution of an atom
containing a number of electrons is divided into shells. The shells, in turn, are thought to consist
of one or more subshells, and subshells are assumed to be composed of one or more orbitals,
which the electrons occupy. While for hydrogen and hydrogen-like systems (such as He+, Li2+,
etc.), all the orbitals within a given shell have the same energy; the energy of the orbitals in a
multi-electron atom depends upon the values of n and l. The lower the value of (n + l) for an
orbital, the lower is its energy. If two orbitals have the same (n + l) value, the orbital with the
lower value of n has the lower energy. In an atom, many such orbitals are possible, and
electrons are filled in those orbitals in the order of increasing energy in accordance with the
Pauli exclusion principle (no two electrons in an atom can have the same set of four quantum
numbers) and Hund's rule of maximum multiplicity (pairing of electrons in the orbitals belonging
to the same subshell does not take place until each orbital belonging to that subshell has got
one electron each, i.e., is singly occupied). This forms the basis of the electronic structure of
atoms.

Exercises

1.​ (i) Calculate the number of electrons that will together weigh one gram. (ii) Calculate the
mass and charge of one mole of electrons.
2.​ (i) Calculate the total number of electrons present in one mole of methane. (ii) Find (a)
the total number and (b) the total mass of neutrons in 7 mg of 14C. (Assume that the
mass of a neutron = 1.675 x 10^-27 kg). (iii) Find (a) the total number and (b) the total
mass of protons in 34 mg of NH3 at STP. Will the answer change if the temperature and
pressure are changed?
3.​ How many neutrons and protons are there in the following nuclei? 13C, 16O, 24Mg,
56Fe, 88Sr
4.​ Write the complete symbol for the atom with the given atomic number (Z) and atomic
mass (A): (i) Z = 17, A = 35. (ii) Z = 92, A = 233. (iii) Z = 4, A = 9.
5.​ Yellow light emitted from a sodium lamp has a wavelength (λ) of 580 nm. Calculate the
frequency (v) and wavenumber (v) of the yellow light.
6.​ Find the energy of each of the photons that: (i) Correspond to light of frequency 3 x
10^15 Hz. (ii) Have a wavelength of 0.50 Å.
7.​ Calculate the wavelength, frequency, and wavenumber of a light wave whose period is
2.0 x 10^-10 s.
8.​ What is the number of photons of light with a wavelength of 4000 pm that provide 1 J of
energy?
9.​ A photon of wavelength 4 x 10^-7 m strikes a metal surface, the work function of the
metal being 2.13 eV. Calculate (i) the energy of the photon (eV), (ii) the kinetic energy of
the emission, and (iii) the velocity of the photoelectron (1 eV = 1.6020 x 10^-19 J).
10.​Electromagnetic radiation of wavelength 242 nm is just sufficient to ionize the sodium
atom. Calculate the ionization energy of sodium in kJ mol^-1.
11.​A 25-watt bulb emits monochromatic yellow light of wavelength 0.57 μm. Calculate the
rate of emission of quanta per second.
12.​Electrons are emitted with zero velocity from a metal surface when it is exposed to
radiation of wavelength 6800 Å. Calculate the threshold frequency (v0) and work
function (W0) of the metal.
13.​What is the wavelength of light emitted when the electron in a hydrogen atom undergoes
a transition from an energy level with n = 4 to an energy level with n = 2?
14.​How much energy is required to ionize an H atom if the electron occupies the n = 5
orbit? Compare your answer with the ionization enthalpy of the H atom (energy required
to remove the electron from the n = 1 orbit).
15.​What is the maximum number of emission lines when the excited electron of an H atom
in n = 6 drops to the ground state?
16.​(i) The energy associated with the first orbit in the hydrogen atom is -2.18 x 10^-18 J
atom^-1. What is the energy associated with the fifth orbit? (ii) Calculate the radius of
Bohr's fifth orbit for the hydrogen atom.
17.​Calculate the wavenumber for the longest wavelength transition in the Balmer series of
atomic hydrogen.
18.​What is the energy in joules required to shift the electron of the hydrogen atom from the
first Bohr orbit to the fifth Bohr orbit, and what is the wavelength of the light emitted when
the electron returns to the ground state? The ground state electron energy is -2.18 x
10^-11 ergs.
19.​The electron energy in the hydrogen atom is given by En = (-2.18 x 10^-18)/n^2 J.
Calculate the energy required to remove an electron completely from the n = 2 orbit.
What is the longest wavelength of light in cm that can be used to cause this transition?
20.​Calculate the wavelength of an electron moving with a velocity of 2.05 x 10^7 m s^-1.
21.​The mass of an electron is 9.1 x 10^-31 kg. If its K.E. is 3.0 x 10^-25 J, calculate its
wavelength.
22.​Which of the following are isoelectronic species, i.e., those having the same number of
electrons? Na+, K+, Mg2+, Ca2+, S2-, Ar
23.​(i) Write the electronic configurations of the following ions: (a) H- (b) Na+ (c) O2- (d) F-
(ii) What are the atomic numbers of elements whose outermost electrons are
represented by (a) 3s1 (b) 2p3 and (c) 3p5? (iii) Which atoms are indicated by the
following configurations? (a) [He] 2s1 (b) [Ne] 3s2 3p3 (c) [Ar] 4s2 3d1.
24.​What is the lowest value of n that allows g orbitals to exist?
25.​An electron is in one of the 3d orbitals. Give the possible values of n, l, and ml for this
electron.
26.​An atom of an element contains 29 electrons and 35 neutrons. Deduce (i) the number of
protons and (ii) the electronic configuration of the element.
27.​Give the number of electrons in the species H2+, H2, and O2+.
28.​(i) An atomic orbital has n = 3. What are the possible values of l and ml? (ii) List the
quantum numbers (ml and l) of electrons for the 3d orbital. (iii) Which of the following
orbitals are possible? 1p, 2s, 2p, and 3f.
29.​Using s, p, d notations, describe the orbital with the following quantum numbers. (a) n =
1, l = 0; (b) n = 3; l = 1; (c) n = 4; l = 2; (d) n = 4; l = 3.
30.​Explain, giving reasons, which of the following sets of quantum numbers are not
possible. (a) n = 0, l = 0, ml = 0, ms = +1/2 (b) n = 1, l = 0, ml = 0, ms = -1/2 (c) n = 1, l =
1, ml = 0, ms = +1/2 (d) n = 2, l = 1, ml = 0, ms = -1/2 (e) n = 3, l = 3, ml = -3, ms = +1/2
(f) n = 3, l = 1, ml = 0, ms = +1/2
31.​How many electrons in an atom may have the following quantum numbers? (a) n = 4, ms
= -1/2 (b) n = 3, l = 0
32.​Show that the circumference of the Bohr orbit for the hydrogen atom is an integral
multiple of the de Broglie wavelength associated with the electron revolving around the
orbit.
33.​What transition in the hydrogen spectrum would have the same wavelength as the
Balmer transition n = 4 to n = 2 of the He+ spectrum?
34.​Calculate the energy required for the process He+(g) → He2+(g) + e-. The ionization
energy for the H atom in the ground state is 2.18 x 10^-18 J atom^-1.
35.​If the diameter of a carbon atom is 0.15 nm, calculate the number of carbon atoms that
can be placed side by side in a straight line across the length of a scale of length 20 cm
long.
36.​2 x 10^8 atoms of carbon are arranged side by side. Calculate the radius of the carbon
atom if the length of this arrangement is 2.4 cm.
37.​The diameter of a zinc atom is 2.6 Å. Calculate (a) the radius of the zinc atom in pm and
(b) the number of atoms present in a length of 1.6 cm if the zinc atoms are arranged side
by side lengthwise.
38.​A certain particle carries 2.5 x 10^-16 C of static electric charge. Calculate the number of
electrons present in it.
39.​In Millikan's experiment, static electric charge on the oil drops has been obtained by
shining X-rays. If the static electric charge on the oil drop is -1.282 x 10^-18 C, calculate
the number of electrons present on it.
 40.​In Rutherford's experiment, generally, the thin foil of heavy atoms, like gold, platinum,
etc., have been used to be bombarded by the α-particles. If the thin foil of light atoms like
aluminum, etc., is used, what difference would be observed from the above results?
41.​Symbols 79Br and 79Br can be written, whereas symbols 35Br and 79Br are not
acceptable. Answer briefly.
42.​An element with a mass number of 81 contains 31.7% more neutrons than protons.
Assign the atomic symbol.
43.​An ion with a mass number of 37 possesses one unit of negative charge. If the ion
contains 11.1% more neutrons than the electrons, find the symbol of the ion.
44.​An ion with a mass number of 56 contains 3 units of positive charge and 30.4% more
neutrons than electrons. Assign the symbol to this ion.
45.​Arrange the following types of radiation in increasing order of frequency: (a) radiation
from a microwave oven, (b) amber light from a traffic signal, (c) radiation from an FM
radio, (d) cosmic rays from outer space, and (e) X-rays.
46.​A nitrogen laser produces radiation at a wavelength of 337.1 nm. If the number of
photons emitted is 5.6 x 10^24, calculate the power of this laser.
47.​Neon gas is generally used in signboards. If it emits strongly at 616 nm, calculate (a) the
frequency of emission, (b) the distance traveled by this radiation in 30 s, (c) the energy
of a quantum, and (d) the number of quanta present if it produces 2 J of energy.
48.​In astronomical observations, signals observed from distant stars are generally weak. If
the photon detector receives a total of 3.15 x 10^-18 J from the radiations of 600 nm,
calculate the number of photons received by the detector.
49.​Lifetimes of the molecules in the excited states are often measured by using a pulsed
radiation source of duration nearly in the nanosecond range. If the radiation source has
a duration of 2 ns and the number of photons emitted during the pulse source is 2.5 x
10^15, calculate the energy of the source.
50.​The longest wavelength doublet absorption transition is observed at 589 and 589.6 nm.
Calculate the frequency of each transition and the energy difference between the two
excited states.
51.​The work function for cesium atom is 1.9 eV. Calculate (a) the threshold wavelength and
(b) the threshold frequency of the radiation. If the cesium element is irradiated with a
wavelength of 500 nm, calculate the kinetic energy and the velocity of the ejected
photoelectron.
52.​The following results are observed when sodium metal is irradiated with different
wavelengths. Calculate (a) the threshold wavelength and (b) Planck's constant.

λ (nm) 500 450 400

v x 10^-5 (cm s^-1) 2.55 4.35 5.35

53.​The ejection of the photoelectron from the silver metal in the photoelectric effect
experiment can be stopped by applying a voltage of 0.35 V when the radiation of 256.7
nm is used. Calculate the work function for silver metal.
54.​If the photon of the wavelength 150 pm strikes an atom and one of its inner bound
electrons is ejected out with a velocity of 1.5 x 10^7 m s^-1, calculate the energy with
which it is bound to the nucleus.
55.​Emission transitions in the Paschen series end at orbit n = 3 and start from orbit n and
can be represented as v = 3.29 x 10^15 (Hz) [1/3^2 - 1/n^2]. Calculate the value of n if
the transition is observed at 1285 nm. Find the region of the spectrum.
56.​Calculate the wavelength for the emission transition if it starts from the orbit having a
radius of 1.3225 nm and ends at 211.6 pm. Name the series to which this transition
belongs and the region of the spectrum.
57.​The dual behavior of matter proposed by de Broglie led to the discovery of the electron
microscope, often used for the highly magnified images of biological molecules and other
types of material. If the velocity of the electron in this microscope is 1.6 x 10^6 m s^-1,
calculate the de Broglie wavelength associated with this electron.
58.​Similar to electron diffraction, neutron diffraction microscopy is also used for the
determination of the structure of molecules. If the wavelength used here is 800 pm,
calculate the characteristic velocity associated with the neutron.
59.​If the velocity of the electron in Bohr's first orbit is 2.19 x 10^6 m s^-1, calculate the de
Broglie wavelength associated with it.
60.​The velocity associated with a proton moving in a potential difference of 1000 V is 4.37 x
10^5 m s^-1. If the hockey ball of mass 0.1 kg is moving with this velocity, calculate the
wavelength associated with this velocity.
61.​If the position of the electron is measured within an accuracy of ± 0.002 nm, calculate
the uncertainty in the momentum of the electron. Suppose the momentum of the electron
is h/4πm x 0.05 nm; is there any problem in defining this value?
62.​The quantum numbers of six electrons are given below. Arrange them in order of
increasing energies. If any of these combinations have the same energy, list them:
63.​n = 4, l = 2, ml = -2, ms = -1/2
64.​n = 3, l = 2, ml = 1, ms = +1/2
65.​n = 4, l = 1, ml = 0, ms = +1/2
66.​n = 3, l = 2, ml = -2, ms = -1/2
67.​n = 3, l = 1, ml = -1, ms = +1/2
68.​n = 4, l = 1, ml = 0, ms = +1/2
69.​The bromine atom possesses 35 electrons. It contains 6 electrons in the 2p orbital, 6
electrons in the 3p orbital, and 5 electrons in the 4p orbital. Which of these electrons
experiences the lowest effective nuclear charge?
70.​Among the following pairs of orbitals, which orbital will experience the larger effective
nuclear charge?
71.​2s and 3s
72.​4d and 4f
73.​3d and 3p
74.​The unpaired electrons in Al and Si are present in the 3p orbital. Which electrons will
experience more effective nuclear charge from the nucleus?
75.​Indicate the number of unpaired electrons in:
76.​P
77.​Si
78.​Cr
79.​Fe
80.​Kr
81.​(a) How many subshells are associated with n = 4? (b) How many electrons will be
present in the subshells having ms values of -1/2 for n = 4?