2.

ATOMIC STRUCTURE
Introduction

This chapter lays the foundations for the explanation of the trends in the physical and chemical properties
of all inorganic compounds. To understand the behavior of molecules and solids we need to understand
atoms.

The atomic theory of matter was first proposed on a firm scientific basis by John Dalton, a British school
teacher in 1808. His theory called Dalton’s atomic theory regarded the atom as the ultimate particle of
matter.

In this unit, we start with the experimental observations made by scientists towards the end of the
nineteenth and beginning of the twentieth century. These established that atoms are made of subatomic
particles, i.e., electrons, protons, and neutrons — a concept very different from that of Dalton.

Dalton’s Atomic Theory:

● Proposed by Dalton in 1808.

● Matter consists of extremely small tiny particles called atoms.
● Atom is the smallest indivisible particle. [Drawback: atoms are divisible into further fundamental
particles like electrons, protons etc.]
● Atoms of the same elements are alike in all aspects like mass, size, volume etc. [Drawback:
discovery of isotopes]
● Atoms of different elements are different in all aspects like mass, size, volume etc. [Drawback:
discovery of isobars]
● Atom is the smallest particle that participates in a chemical reaction.
● Atoms cannot be created or destroyed in a chemical reaction.
● Atoms of the same elements or different elements combine together to form compound atoms
/molecules in the same proportion of mass.

2.1 Discovery of Fundamental Particles:

Discovery of the electron:

Discovered by Sir J. J. Thomson by Cathode ray tube experiment.

Cathode ray tubes are sealed glass tubes and have very little air inside. Two electrodes are placed
at the ends of the cathode ray tube and a high electric potential is applied. A particle beam
originates from a cathode conducting towards the anode. Cathode rays were detected by placing
phosphorus at a distance beyond the anode. The phosphorus is emitted by the impaction of the
cathode rays.

30
 Atomic structure

These rays themselves are not visible but their behavior can be observed with the help of certain
kinds of materials (fluorescent or phosphorescent) which glow when hit by them. Television
picture tubes are cathode ray tubes and television pictures result due to fluorescence on the
television screen coated with certain fluorescent or phosphorescent materials.

When two oppositely charged electric plates are placed around the cathode ray, the ray is observed
to be deflected towards the positively charged plate indicating it is negative in nature.

Cathode rays consist of extremely small negatively charged particles called negatrons [ term
“electron” is given by G. J. Stoney]

The calculated e/m ratio or specific charge is found to be -1.76 * 108 C/g

The e/m ratio of the cathode ray is independent of the nature of the gas and the nature of the
electrode used in the discharge tube. Therefore, the electron is considered to be a fundamental
particle.

R. A. Millikan calculates the mass of electrons through the oil drop experiment. The mass of
electron is = 9.1 * 10-28 g.

Millikan oil-drop experiment:

● In this method, oil droplets in the form of mist, produced by the atomizer, were allowed to
enter through a tiny hole in the upper plate of the electrical condenser.
● The downward motion of these droplets was viewed through the telescope, equipped with a
micrometer eyepiece.
● Millikan was able to measure the mass of oil droplets by measuring the rate of fall of these
droplets. The air inside the chamber was ionized by passing a beam of X-rays through it.
● The electrical charge on these oil droplets was acquired by collisions with gaseous ions. The
fall of these charged oil droplets can be retarded, accelerated, or made stationary depending

31
 Atomic structure

upon the charge on the droplets and the polarity and strength of the voltage applied to the
plate.
● By carefully measuring the effects of electric field strength on the motion of oil droplets,
Millikan concluded that the magnitude of electrical charge, q, on the droplets is always an
integral multiple of the electrical charge, e, that is, q = ne, where n = 1, 2, 3…

Discovery of protons:

● Discovered by Sir E. Goldstein by anode ray experiment [Ernst Rutherford gives term proton
through gold foil experiment]
● Setup was similar to the cathode-ray experiment.
● Anode rays and cathode rays are simultaneously generated due to the ionization of gases at
very high potential.
● Anode rays consist of positively charged particles [deflection towards negatively charged
electric plate].
● For hydrogen gas, the e/m ratio of anode ray is found to be maximum.

Discovery of Neutrons:

● Proposed by Sir Ernest Rutherford and discovered by James Chadwick alpha particle scattering
experiment.

Gold foil experiment / Alpha particle scattering experiment:

● Ultrathin sheets (thickness ∼ 100 nm) of gold foil are bombarded with fast-moving alpha particles.
The gold foil is surrounded by a screen which allows the detection of the deflected particles. [Gold
is selected due to its highest malleability and it is heavier.
● Alpha particle emitter is surrounded by Lead block so that lead can absorb radiation.
● Very few alpha particles deflected by an angle less than 90◦. Maximum alpha particles passed
through the gold foil without any deflection.

32
 Atomic structure

● One in around 20,000 alpha particles deflected by 180◦.

Chadwick did the same experiment by bombarding alpha particles with ultrathin beryllium sheets.
When electrically neutral particles having a mass slightly greater than that of protons were emitted.
He named these particles neutrons.

2.2 Atomic Models: -

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

● to account for the stability of atoms,

● 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 and,
● to understand the origin and nature of the characteristics of electromagnetic radiation
absorbed or emitted by atoms

I. Thomson’s Atomic Model:

● Also known as Plum- Pudding Model.

● Electrons are embedded in the sea of positive charge so that the atom is electrically neutral
as a whole. Electrons are like a plum in a pudding.

33
 Atomic structure

Drawbacks:

● Could not explain the nucleus part of an atom and scattering experiment of Rutherford.

● Could not explain the stability of atoms or how protons hold electrons inside.

II. Nuclear Atomic Model:

● Proposed by Rutherford based on experimental results obtained in Alpha particle scattering

experiment.
● An atom has two parts – the nuclear part and the extranuclear part.
● The nuclear part is located centrally in a small volume having almost the entire mass and whole
positive charge concentrated.
● The extranuclear part consists of electrons revolving around the nucleus in circular pathways.
● The size of an atom is 10-10 m and the size of the nucleus is 10-15 m.
● All elements have almost the same density [ approx..1014 g/cc]

34
 Atomic structure

Drawbacks:

● Failed to explain the stability of atoms as by classical theory of electrodynamics by J. C. Maxwell,

whenever a charged particle accelerates or oscillates within the electric field, it constantly emits
electromagnetic radiation. Therefore, the electron should be emitting electromagnetic radiation
constantly and fall into the nucleus in 10-8 seconds following a spiral path as it will lose energy by
radiation leading to a gradual decrease in the radius of its circular path.
● Failed to explain definite lines on the hydrogen.

2.3 THEORIES

E.M Wave theory:

● Radiant energy is emitted/ absorbed continuously in the form of an electromagnetic wave as it

consists of an electric field and a magnetic field.
● A wave is a periodic disturbance in space in or in a medium that involves the elastic displacement
of material particles or periodic variation of some physical quantities like pressure, electric field,
temperature, magnetic field, etc.
● All kinds of electromagnetic radiations travel with the same speed i.e. the speed of light in a
vacuum.
● No medium is required for propagation.
● Energy associated with electromagnetic radiation is directly proportional to the intensity
● Frequency * wavelength = speed of light

Drawbacks: It fails to explain:

A. photoelectric effect
B. blackbody radiation
C. Variation of heat capacity of monatomic solid with temperature.
D. Compton effect
E. Discontinuous spectrum

Planck’s Quantum Theory:

● absorbed discontinuously in the form of packets/chunks of energy called quanta. For light, such
energy packets are called photons and for heat, they are phonons.

● Energy associated with the quanta of radiation is directly proportional to the frequency of radiation.
E = hν (where h= Planck’s constant)
● Total energy absorbed or emitted is an integral multiple of hν.

Photoelectric effect:

● Given by Hertz.
● The phenomenon of emission of photoelectrons from a metal surface when the light of suitable
frequency falls on it.

35
 Atomic structure

● The work function of a metal is defined by the minimum energy required to just free the electron
from the metal surface by overcoming its binding energy.
● No electrons are ejected unless their frequency exceeds a threshold value characteristic of the
metal.
● The kinetic energy of the ejected electrons increases linearly with the frequency of the incident
radiation but is independent of the intensity of the radiation.
● Even at low light intensities, electrons are ejected immediately if the frequency is above the
threshold.
● Photoelectric effect is only given by group-1 elements.
● Lithium doesn’t show a photoelectric effect due to its small size.
● Stopping potential is the minimum potential applied to just stop the electron after ejection is made
its kinetic energy is finally zero.

Blackbody Radiation:

● It is the phenomenon of color change due to the heating of an object.

● Any object emitting or absorbing all kinds of radiation is called a black body. Hence, the black
body is a perfect emitter as well as a perfect absorber.
● Energy density, dE, is the total energy in a region of the electromagnetic field divided by the
volume of the region due to all the oscillators corresponding to wavelengths between λ and λ + dλ.
This energy density is proportional to the width, dλ, of this range, and is written –

dE = ρ(λ, T) dλ

where ρ is a constant of proportionality between dE and dλ, is called density of states.

● Blackbody radiation is the thermal electromagnetic radiation within or surrounding a body in

thermodynamic equilibrium with its environment emitted by a blackbody.

36
 Atomic structure

The graph for blackbody radiation is:

● It has a specific spectrum of wavelengths, inversely related to the intensity that depends only on
the temperature of the body which is assumed to be uniform and constant.
● Physicist Rayleigh regarded the presence of radiation of frequency ν as signifying that the
electromagnetic oscillator of that frequency had been excited.
Eavg = average energy of each oscillator = KT where K = Boltzmann’s constant.

● Rayleigh-Jeans law:

ρ(λ, T) = 8πKT/λ⁴

But this fails for high frequencies as λ increases ρ decreases significant. Therefore, without going
through a maximum, an oscillator of short wavelength is excited even at room temperature which
phenomenon is known as Ultraviolet Catastrophe.

37
 Atomic structure

The graph for Rayleigh-Jeans law is:

● Planck distribution

8πℎ𝑐
ρ(λ, 𝑇) =
( ℎ𝑐
𝑒λ𝑘𝑇 −1 λ ) 5

ℎ𝑐
For long wavelengths, λ𝑘𝑇
<<1

ℎ𝑐 ℎ𝑐
𝑒λ𝑘𝑇 − 1≈ λ𝑘𝑇

Therefore, Planck’s distribution was reduced to Rayleigh-Jeans law.

The graph for Planck’s Distribution is:

38
 Atomic structure

2.4 Heat Capacities:

● According to Dulong-Petit’s law, the mean energy of an atom as it oscillates about its mean position
in a solid is kT for each direction of displacement. As each atom can oscillate in three dimensions,
the average energy of each atom is 3kT;
● for N atoms the total energy is 3NkT.
● The contribution of this motion to the molar internal energy is, therefore,
Um = 3NAkT = 3R
● The molar constant volume heat capacity is the

𝐶𝑉,𝑚 = ( )
∂𝑈
∂𝑇
𝑉

● It was found that the molar heat capacities of all monatomic solids are lower than 3R at low
temperatures; the values approach zero as T →0.
● Einstein formulated the decrease of heat capacity at low temperatures.
● At low temperatures, only a few oscillators possess enough energy to oscillate significantly, so the
solid behaves as though it contains far fewer atoms than is actually the case.

2.5 Compton effect:

● Discovered by Arthur Holly Compton.

● Photons exhibit wave-particle duality.
● The energy of photons is directly proportional to their frequency and inversely proportional to their
wavelength.
● In the Compton effect, individual photons collide with single electrons that are free or loosely
bound in matter atoms. Colliding photons transfer some of their energy and momentum to the
electrons, which in turn recoil. In the instant of the collision, new photons of less energy and
momentum are produced that scatter at angles the size of which depends on the amount of energy
lost to the recoiling electrons.
● Because of the relation between energy and wavelength, the scattered photons have a longer
wavelength. It also depends on the size of the angle through which the X-rays were diverted. The
increase in wavelength, or Compton shift, does not depend on the wavelength of the incident
photon.

2.6 Spectrum:

● The impression is obtained on the photographic plate when the radiations of particular wavelengths
are analyzed through the prism.
● Spectrums are of two kinds:

Emission spectrum:

● a spectrum of emitted light from the source by

● heating the substance into the flame
● Passing electric discharge through the substance in the vapour phase.
39
 Atomic structure

● Passing the current through the filament of high melting point metal.
● The emission spectrum is further classified into a continuous and discontinuous spectrum.
● A continuous spectrum is obtained due to radiation emitted by the light source. Like sun, candle,
etc.
● Discontinuous spectrum is further classified into line spectrum (atomic spectrum) and band
spectrum (molecular spectrum) e.g., emission spectra for nobel gases.

The emission spectrum of Nobel gases

Absorption Spectrum:

White light consisting of all wavelengths is first passed through substances and then analyzed through a
prism.

40
 Atomic structure

● The emission spectrum and absorption spectrums are complementary to each other.
● Spectrums are characteristics of elements i.e. unique to every element.
● Hydrogen emission spectrum:

Hydrogen gas is in a sealed tube at low pressure and two electrodes are attached. An electric
potential of 10,000 volts is applied.

One bluish light falls upon the prism and the emission spectrum is obtained on the photographic
plate.

2.7 Bohr’s Atomic Model:

A. Based upon the concept of quantization [ Quantization:- when only discrete values are acceptable.
B. Electrons revolve around the nucleus in a circular path called an orbit.
C. As the electron keeps on moving in an orbit, it never loses the energy; the energy remains fixed.
These orbits are called stationary orbits or fixed energy levels.
D. Out of an infinite possible circular path around the nucleus, electrons choose to revolve on that path
for which its angular momentum is quantized, then only its energy remains fixed
mvr = nh/2𝝿
E. The energy levels are represented by integers known as quantum numbers. The range of quantum
numbers starts from the nucleus side with n=1 having the lowest energy level. The orbits are
assigned as K (n=1), L (n=2), M (n=3) , N (n=4) etc. shells .
F. When an electron is in the lowest energy level, it is said to be in the ground state.
G. The electrons move from a lower energy level to a higher energy level by gaining the required
energy and an electron moves from a higher energy level to a lower energy level by losing energy.
Derivations of Bohr’s Atomic Model:

41
 Atomic structure

Representation of Bohr’s Atomic Model:

Derivations of equations of Bohr’s Atomic Model:

Bohr began with a classical mechanical approach assuming that the electron in a one-electron atom is
moving in a circular orbit with a radius, r, from the nucleus.

The movement of an electron in its orbit will cause a centrifugal force giving it a tendency to fly away
from the nucleus. This force is given by

Fcentrifugal = -mv2 / r [ where m is the mass of the electron, and v is its velocity.]

For stability of the atom, this centrifugal force should be exactly matched by an opposing centripetal force,
drawing the electron inward through the coulombic attraction between the electron’s negative charge and
the positive charge in the nucleus. This coulombic force of attraction is given by

FCoulombic = -Ze2 / r2

By equating both the forces we get,

mv2 / r = Ze2 / r2

And we get,

r = mv2r2/ Ze2 = (mvr)2 / mZe2

We know, mvr = nh/2π

42
 Atomic structure

Therefore, we can write

r = n2h2/ 4π2mZe2

For hydrogen, Z=1,

Radius of hydrogen= a0 = 0.529 Å

For a radius of anyone electron, we can write,

r = n2a0 / Z

The radius increases in direct proportion to the square of the quantum number, n2 , and decreases in inverse
proportion to the atomic number, Z. Thus, the sizes of the orbits in hydrogen are predicted to be a0, 4a0, 9a0,
16a0, 25a0, etc

The kinetic energy, which arises from electron motion, is K = ½mv2 . The potential energy, which arises
from the coulombic attraction between the negative charge of the electron and the positive charge in the
nucleus, is given by U = –Ze2 /r.

Therefore,

E = K + U = ½ mv2 - Ze2/ r

mv2 = -Ze2/ r ( obtained from previous equations)

Therefore, E = - ½ Ze2/r

The negative sign in equation (9) indicates favorable energy of attraction, which must be overcome to
remove the electron to an infinite distance from the nucleus.

Putting value of r we get,

E = -2𝝿2mZ2e4 / n2h2

So, E = -BZ2/n2

Hence, the energy becomes more favorable (negative) in direct proportion to the square of the nuclear
charge, and less favorable (less negative) in inverse proportion to the square of the quantum number.

43
 Atomic structure

The only way the atom can assume a lower-energy state is through the emission of energy in the form of
electromagnetic radiation. The energy of this radiation is equal to the energy difference between the high
state and the lower state:

Elight = | Efinal - Einitial| = | Elow - Ehigh|

From Planck, we know that E = hν, so if we divide through equation (12) by h we can write an expression
for the frequencies of the emitted light:

𝞶 = BZ2/h [ 1/ nlow2 - 1/ nhigh2 ]

BZ2/h = R = Rydberg constant = 10973731.6 m-1

nlow Region Series name

1 Ultraviolet Lyman

2 Visible Balmer

3 Infrared Paschen

4 Infrared Brackett

5 Infrared Pfund

Drawbacks of Bohr’s Atomic Model:

● Bohr’s model of an atom failed to explain the Zeeman Effect (effect of magnetic field on the
spectra of atoms).
● It also failed to explain the Stark effect (effect of electric field on the spectra of atoms).
● It violates Heisenberg's uncertainty principle.
● It could not explain the spectra obtained from larger atoms.

2.8 Heisenberg’s Uncertainty Principle:

● Heisenberg’s uncertainty principle states that it is impossible to measure or calculate exactly, both
the position and the momentum of an object.

● It holds significant importance in the quantum world.

● Supports the wave-particle duality theory.

44
 Atomic structure

Δx Δp ≥ h/4π

2.9 De-Broglie Equation and wave-particle duality:

● The joint particle and wave character of matter and radiation is termed wave-particle duality.

● The wave nature of particles is seen in electron diffraction experiments by the Davisson-Germer
Experiment. E = hν = hc/ 𝝀 = mv2

Therefore, de-Broglie wavelength(𝝀) = h/mv

This is known as the de-Broglie equation.

2πr = n𝝀 Or, 1/𝝀 = n/2πr

Substituting the value of 𝝀, we get, mv = nh/ 2πr Which supports Bohr’s postulate of angular
momentum.

Sommerfeld’s atomic model:

● Electrons move around the nucleus in a circular or elliptical path.

● The electron exists in the electron current form.

● One or more sublevels of the same energy level can exist from the second energy

● The eccentricity of the orbit gave rise to a new quantum number that determines the shape of the
orbitals: the azimuthal quantum number. During elaboration, a principal quantum number n = n '+
k. The secondary quantum number n 'determines the ellipse's angular (radial) momentum and
eccentricity. For n '= 0 circular orbits arise. The lateral quantum number k describes the angular
momentum that the hydrogen electron can take.

45
 Atomic structure

● Included relativistic effects, since electrons can move with speeds quite close to that of lithium.

Drawbacks:

● Only applicable to mono-electronic species.

● Did not describe the electronic distribution.

● The model allowed us to calculate the energies of the allowed states and the frequencies of the
radiation emitted or absorbed in the transitions between states, without giving information about the
times of these transitions.

● Now it is known that electrons do not follow trajectories with predetermined shapes such as orbits,
but rather occupy orbitals, regions of space that correspond to solutions of the Schrodinger equation

● He did not manage to explain the anomalous Zeeman effect.

2.10 Quantum-mechanical concept on Atomic structure:

Quantum Numbers: Set of numbers as identification numbers for an electron/orbital i.e. with the
help of quantum number, we can get all the information about the electron or orbital like energy,
distance, shape, orientation, etc In absence of electric and magnetic field orbitals of particular subshells
have the same energy hence called a degenerate orbital.

46
 Atomic structure

I. Principle Quantum Number:

● Given by Bohr.
● It denotes the main energy level called orbit or shell.
● Represented by n.

II. Azimuthal/ subsidiary quantum number / angular momentum quantum number:

● Given by Sommerfeld.
● It denotes the sub-energy level present in the main energy level called subshell.
● It gives the idea of the shape of the orbital.
● Represented by l.
● Its value is from 0 to (n-1)
● s- subshell for l = 0
● p-subshell for l = 1
● d-subshell for l=2
● f-subshell for l=3
● g-subshell for l=4

III. Orbital angular momentum = 𝑙(𝑙 + 1) * h/2π

IV. Magnetic quantum number:

● It is given to explain the Zeeman and Stark Effect.

● It tells about the orientation and direction of the electron or orbital.
● It is denoted by “m”.
● Its value is from -l to +l including 0.
● l=0, m =0 denotes s-subshell.
● l=1, m= -1, 0, 1 denotes px, py, pz.
● Number of orbitals present in a subshell = 2l+1
● Maximum number of electrons in a subshell = 2(2l +1)
● Maximum number of electrons in a shell = 2n2 (maximum = 32)
● Number of subshells in a shell = n

Spin quantum number:

● Given by Uhlenbeck and Goudsmit.

● It denotes the spin of the electron in an atom.
● It is represented by s.
● The magnitude of spin angular momentum: 𝑠(𝑠 + 1). ℎ/2π

47
 Atomic structure

● By convention, s = +½ is anticlockwise and s = -½ is clockwise.

2.11 Aufbau Principle:

● Electron starts filling with the lower energy subshell first and then progressively starts filling to the
higher energy subshell.

● Bohr-Bury scheme for the multi-electron system:

A. The electrons are arranged around the nucleus in different energy levels or energy shells. The electrons
first occupy the shell with the lowest energy i.e., closest to the nucleus.
B. K shell (n=1) can only take up to 2 electrons. L shell (n=2) can take up to 8 electrons. [number of
electrons = 2n2]
C. The outermost shell of an atom cannot have more than 8 electrons and the shell next to the outermost
shell cannot have more than 18 electrons.

● Subshells having a relatively smaller (n+l) value will have lower energy.
● If (n+l) values ties, then a subshell having smaller ‘n’ will have lower energy.
● The order of filling of electrons according to Aufbau Principle depending on their energy can be
represented as:

Drawbacks:

A. It does not talk about the order of filling of electrons in the different orbitals in the
subshells.

48
 Atomic structure

B. It could not explain the electronic configuration of Chromium [Cr24 = [Ar]3d54s1] and
Copper [ Cu29 = [Ar]3d104s1]

2.12 Hund’s Rule of Maximum Spin Multiplicity:

● In a subshell, for a given electron configuration, the electrons can be filled in the order so
that the lowest energy term is the one with the greatest value of spin multiplicity.
● Based on the observations on atomic spectra.
● Spin multiplicity = 2S+ 1, where S=total spin
● Every orbital in the subshell must be singly occupied before the pairing of the electrons in
an orbital.
● For the maximization of total spin, all electrons in a single occupancy orbital have the same
spin.
● The electrons present in singly occupied orbitals possess identical spin.

2.13 Pauli’s Exclusion Principle:

● In an atom, all the four quantum numbers for any two electrons can not be the same and if
n, m, m are the same then s must be different.
● Any orbital can accommodate a maximum of 2 electrons with opposite spin.
● Most stable arrangement is th e maximum spin multiplicity arrangement.
● In a degenerate orbital, electrons enter singly with the same spin first and then the pairing of
electrons starts.

2.14 Electronic configuration:

● The distribution of electrons in various energy levels in atoms.

● Electronic configuration = nlx where n and l are quantum numbers and x is the number of
electrons in various energies.
● Extra Stability of half-filled and full-filled subshell is due to:
1. Symmetrical distribution.
2. Exchange energy. [ Number of exchanges is directly proportional to exchange energy
which increases the stability of the atom/ molecules]
3. Number of exchanges made by electron with the same spin only = n(n+1) /2

Classification of substance on the basis of their magnetic interaction:

● Substance is classified into diamagnetic and paramagnetic categories.

● Diamagnetic substances are weakly repelled by magnetic fields and all electrons are paid in
that substance.

49
 Atomic structure

● Paramagnetic substances are weakly attracted by magnetic fields and they must contain at
least one unpaired electron.
● Paramagnetism is directly proportional to the number of unpaired electrons.
● Spin only magnetic moment (𝝁s) = 𝑛(𝑛 + 2) where n = number of unpaired electrons.
● Orbital angular momentum = 𝑙(𝑙 + 1) BM

2.15 Wave Mechanical approach:

Schrödinger Atomic Model:

● Given by Schrödinger.
● Assumed electrons to be a three-dimensional stationary wave (matter wave) moving in the
electric field of the nucleus.
● Derived an equation in quantum mechanics to describe the wave motion of electrons. It is a
partial differential equation that describes the dynamics of quantum mechanical systems via
the wave function. The trajectory, positioning, and energy of these systems can be retrieved
by solving this equation.
2 2
ħ 𝑑ψ
− 2𝑚 𝑑𝑥2
+ 𝑉(𝑥)ψ = 𝐸ψ
where V(x) is the potential energy of the particle at point x; E(x) is the total energy of the
particle at point x; ħ = h/2π

● Described 𝜳 as the orbital function or wave function or amplitude function.

𝜳n,l,m represents the electronic motion where n, l, and m are the quantum numbers.
Example: 𝜳,4,2,o represents 4z2 orbital.
● Upon solving the Schrӧdinger equation, many solutions are obtained in which few of them
are selected by applying the boundary conditions.

Boundary conditions:

A. 𝜳 must be continuous.
B. 𝜳 must be finite infinite span.
C. 𝜳 must be single-valued.
D. There must be no sudden change in 𝜳.
E. Total probability density of 𝜳 between -∞ to ∞ must be 1.
∞
∫ Ψ 2.dx.dy.dz = 1
−∞

● Acceptable solutions of 𝜳 are called Eigen functions and total energy(E) corresponding to it
is called Eigenvalues.
● Acceptable solutions of 𝜳 are mathematical equations in terms of x, y, z i.e. Cartesian
Coordinate system.

50
 Atomic structure

𝜳 = f(x, y, z)
For better interpretation of 𝜳, it is converted into spherical coordinate system as atom is
spherical.
● According to him, an isolated atom has no boundary i.e. an electron can be found
everywhere between nucleus and infinity.
● s orbital is the only orbital in which the electron density is maximum at its surface of nucleus
whereas in case of p, d and f orbital, electron density is zero at the surface of the nucleus.
● According to Bohr, the electron could be found only at a distance of 0.529 Å but
Schrödinger suggested that the probability of finding electron is possible all places from 0 to
infinity but the probability of finding electron is maximum at a distance of 0.529 Å.

2.16 The time-independent Schrodinger Equation:

For an isolated atom or molecule, the forces acting depend only on the coordinates of the charged
particles of the system and are independent of time. Therefore, the potential energy V is
independent of t for an isolated system. For systems where V is independent of time, the
time-dependent Schrodinger equation has solutions of the form ψ(x1,......,zn,t)=f(t)ψ(x1,......,zn,t)
where ψ is a function of the 3n coordinates of the n particles and f is a certain function of time. We
shall demonstrate this for a one-particle, one-dimensional system.

For a one-particle, one-dimensional system with V independent of t, Schrodinger Eq. becomes

2 2
ħ ∂ψ ħ ∂ψ
− 2𝑚 ∂𝑥2
+ 𝑉(𝑥)ψ =− 𝑖 ∂𝑡
..(17.18)

Let us look for the solutions of (17.18) that have the form

ψ(x,t)=f(t)ψ(x) ..(17.19)

We have ∂2ψ/∂x2 = f(t) d2ψ/dx2 and ∂ψ/∂t = ψ(x)df/dt. Substitution into (17.18) followed by
division by fψ=ψ gives

2 2
ħ ∂ψ ħ 1 𝑑(𝑓)
− 2𝑚 ∂𝑥2
+ 𝑉(𝑥)ψ =− 𝑖 𝑓(𝑡) 𝑑𝑡
= 𝐸 ..(17.20)

Where the parameter E was defined as E = -(ħ/i)f’(t)/f(t)

From the definition of E, it is equal to a function of t only and hence is independent of x. However,
the above equation shows that

E=-(ħ2/2m)ψn(x)/ψ(x)+V(x), which is a function of x only and is independent of t.

51
 Atomic structure

Hence, E is independent of t as well as independent of x and must therefore be constant. Since the
constant E has the same dimensions as V, it has the dimensions of energy. Quantum mechanics
postulates that E is in fact the energy of the system:

Eq (17.20) gives
df/f=-(iE/ħ)dt,

which integrates to
lnf = -iEt/ħ+C.

Therefore, f=eCe-iEt/ħ= Ae-iEt/ħ, where A=eC is an arbitrary constant.

The constant A can be included as part of the ψ(x) factor, so we omit it from f. Thus

f(t)=e-iEt/h ..(17.21)

Equation (17.20) also gives

2 2
ħ 𝑑 ψ(𝑥)
− 2𝑚 2 + 𝑉(𝑥)ψ(𝑥) = 𝐸ψ(𝑥) …(17.22)
𝑑𝑥

Which is the (time-independent) Schrodinger equation for one particle, one-dimensional system.
Equation (17.22) can be solved for ψ when the potential-energy function V(x) has been specified.

For an n-particle, three-dimensional system, the same procedure that led to Eqs. (17.19), (17.20),
and (17.22) give ψ=e-iEt/ħψ(x1,y1,z1,....,xn,ynzn) -(17.23)

Where the function ψ is found by solving

−
2
ħ
2𝑚1 ( 2
𝑑ψ
𝑑𝑥1
2 +
2
𝑑ψ
𝑑𝑦1
2 +
2
𝑑ψ
𝑑𝑧1
2
)
.... −
2
ħ
2𝑚𝑛 ( 2
𝑑ψ
𝑑𝑥𝑛
2 +
2
𝑑ψ
𝑑𝑦𝑛
2 +
2
𝑑ψ
𝑑𝑧𝑛
2
) + 𝑉ψ = 𝐸ψ ~(17.24)

.
The solutions ψ to the time-independent Schrodinger equation (17.24) are the (time-independent)
wave functions. States which Ψ is given by (17.23) are called stationary states. We shall see that for
a given system there are many different solutions to (17.24), different solutions corresponding to
different values of the energy E. In general, quantum mechanics gives only probabilities and not
certainties for the outcome of a measurement. However, when a system is in a stationary state, a
measurement of its energy is certain to give the particular energy value that corresponds to the
wave function ψ of the system. Different systems have different forms for the potential-energy
function V(x1,….,zn), and this leads to different sets of allowed wave functions and energies when
(17.24) is solved for different systems. All this will be made clearer by the examples in the next few
sections.

52
 Atomic structure

2
For a stationary state, the probability density |Ψ| becomes

2 2 𝑖𝐸𝑡/ħ −𝑖𝐸𝑡/ħ 0 2
|Ψ| = |𝑓ψ| = (𝑓ψ) * 𝑓ψ = 𝑓 * ψ * 𝑓ψ = 𝑒 ψ *𝑒 ψ = 𝑒 ψ * ψ = |ψ| (17.25)

Where we used (17.19), (17.21) and the identity

(fψ)* = f*ψ* (prob.17.19)

2 2
Hence, for a stationary state, |Ψ| = |ψ| , which is independent of time. For a stationary state, the
probability density and the energy are constant with time. There is no implication, however, that the
particles of the system are at rest in a stationary state.

It turns out that the probabilities for the outcomes of measurements of any physical property
involve |Ψ|, and since |Ψ| = |ψ|, these probabilities are independent of time for a stationary state.
−𝑖𝐸𝑡/ħ
Thus, the 𝑒 factor in (17.23) is of little consequence, and the essential part of the state function
for a stationary state is the time-independent wave function ψ(x1,….,zn). For a stationary state, the
2
normalization condition (17.17) becomes ∫|ψ| 𝑑τ = 1, where ∫𝑑τ denotes the integral over all
space.

The wave function ψ of a stationary state of energy E must satisfy the time-independent
Schrodinger equation (17.24). However, quantum, mechanics postulates that not all functions that
satisfy (17.24) are allowed as wave functions of the system. In addition to being a solution of
(17.24), a wave function must meet the following three conditions: (a) the wave function must be
single-valued. (b) The wave function must be continuous. (c) The wave function must be
quadratically integrable. Condition (a) means that ψ has one and only one value at each point in
space. The function of a one-particle, one-dimensional system. Condition (b) means that ψ makes
no sudden jumps in value. A function like that in Fig.17.6b is ruled out. Condition (c) means that
2
the integral over all space ∫|ψ| 𝑑τ is a finite number. The function x2 (fig.17.6c) is not
∞ ∞
4 5
quadratically integrable, since ∫ 𝑥 𝑑𝑥 = 𝑥 /5 [ ]−∞ = ∞ − (− ∞) = ∞. Condition (c) allows
−∞
2
the wave function to be multiplied by a constant that normalizes it, that is, that makes ∫|ψ| 𝑑τ = 1
. [If ψ is a solution of the Schrodinger equation (17.24), then so is kψ, where k is any constant; see
Prob.17.20]. A function obeying conditions (a), (b), and (c) is said to be well-behaved.

Since E occurs as an undetermined parameter in the Schrodinger equation (17.24), the solutions ψ
that are found by solving (17.24) will depend on E as a parameter: ψ = ψ(x1,….,zn;E). It turns out
that ψ is weel-behaved only for certain particular values of E, and it is these values that are the
allowed energy levels.

53
 Atomic structure

2.17 Real hydrogen-like Wave functions for n=1 and n=2

−1/2 3/2 −𝑍𝑟/𝑎

1𝑠 = π (𝑍/𝑎) 𝑒
−1/2 3/2 −𝑍𝑟/2𝑎
2𝑠 = 1/4(2π) (𝑍/𝑎) (2 − 𝑍𝑟/𝑎)𝑒
−1/2 5/2 −𝑍𝑟/2𝑎
3𝑠 = 1/4(2π) (𝑍/𝑎) 𝑟𝑒
−1/2 5/2 −𝑍𝑟/2𝑎
𝑠𝑖𝑛θ𝑐𝑜𝑠ϕ4𝑠 = 1/4(2π) (𝑍/𝑎) 𝑟𝑒
−1/2 5/2 −𝑍𝑟/2𝑎
𝑠𝑖𝑛θ𝑠𝑖𝑛ϕ5𝑠 = 1/4(2π) (𝑍/𝑎) 𝑟𝑒 𝑐𝑜𝑠θ

2.18 Max Born Interpretation:

1. It states the probability density of finding a given particle at a given point or region is directly
proportional to the square of the magnitude of the particle wavefunction at that point.
Probability density = |𝜳|2 = 𝜳𝜳* where 𝜳* is the complex conjugate of the wavefunction 𝜳. The
product of 𝜳 and 𝜳* yields the real value.
2. 𝜳r = R(r) is the radial wave function and 𝜳r2 = R2(r) is the radial probability density. 𝜳r2 tells
about the probability of finding an electron at a distance r in d𝜏 volume
d𝜏 = dx. dy. dz
3. 𝜳r2 dv = R2(r).dv is the radial distribution function which tells us about the total probability of
finding the electron in an enclosed spherical volume dv at distance ‘r’.
4. Radial electronic density for different orbitals can be represented as :

Fig. wave function and probability for the lowest three particles in a box stationary state.

54
 Atomic structure

But 𝜳 vs r graph has no practical significance.

5. The peak of the graph signifies the most probability of finding the electron and the corresponding
r-value is called as maximum probable distance or most probable distance.
6. For 1s orbital, the most probable distance is at a0.
For 2s orbital, the most probable distances are at 0.77a0 and 5.239a0 and the least probable distance
is at 2a0. The radial nodes are present at these least probable distances.
For 2p orbital, the most probable distance is at 4a0.

2.19 Radial node / Spherical Node:

It is a spherical surface at which the probability of finding electrons is 0 everywhere. A radial node is a
spherical surface at which the sign of the wave function changes.
An orbital is a three-dimensional region around the nucleus in which the probability of finding an electron
is maximum i.e. 90-95% which consists of only a few Å.

➔ Radial node= n-l-1

55
 Atomic structure

𝜳 = R(r)𝚹(𝝷)Ⲫ(ⲫ).

➢ R(r) is a function of n and l.

➢ 𝚹(𝝷) is a function of l and m.
➢ Ⲫ(ⲫ) is a function of m.
➢ 𝚹(𝝷)Ⲫ(ⲫ) = Angular wave function.
➢ [𝚹(𝝷)Ⲫ(ⲫ)]2 = angular probability density.

➔ For ns orbital
[𝚹(𝝷)Ⲫ(ⲫ)]2 = 1/ 4π = constant.

Therefore, s orbital is directionless and orientation-less.

For p orbital, the angular probability density is a function of cos𝚹.

Therefore, in the case of p, d, and f orbital, the probability of finding electron or electron density varies
with the direction. So, these are directional orbitals.

Radial nodes for s orbital:

● Angular node:

It is any surface or plane passing through an origin at which the electron density is zero.
Angular node = l

As n increases, the size of the orbital increases but the shape remains the same.
Angular nodes for p orbitals are :

56
 Atomic structure

Angular nodes for d orbitals:

Therefore, Total number of nodes = radial nodes + angular nodes

Total Number of nodes = n-l-1 + l = n-1

57
 Atomic structure

Key Points:

● Isotopes differ physically while maintaining the same chemical properties.

● Different isotopes have different values for e/m.
● Isobars don't have the same physical and chemical characteristics.
● Isobars don't all have the same e/m value.
● A1 - Z1 for isotones equals A2 - Z2
● A1 - 2Z1 for iso-diapher equals A2 - 2Z2
● Only the monoelectronic species like H, He+, Li2+, Na10+, U91+ etc can be described by Bohr’s
atomic model.
● Kinetic energy and de-Broglie wavelength:

K.E. = ½ mv2 or m x KE = ½ m2v2 or mv = 2𝑚𝐾. 𝐸.

λ = h/mv ⸫ λ = h/ 2𝑚𝐾. 𝐸.
● When a charged particle carrying Q coulomb charge is accelerated by applying potential
difference of V volts, then:

KE = Q.V joule

λ = h/ 2𝑚𝐾. 𝐸. = λ = h/ 2𝑚𝑄𝑉
● Experimental proof of the electron's wave-like character was provided by Davisson and Germer.
● Although the de Broglie theory holds true for both macroscopic and microscopic objects, it has
no physical relevance for macroscopic items

58
 Atomic structure

Formula Sheet

● Closest distance of approach of α-particles: R = 4KZe2 / mα Vα2

● Radius of a nucleus: R = R0 A1/3 cm
● Photo electric effect: hν = hνo + ½ mev2
● Planck’s quantum theory: Energy = hν = hc/ λ
● Rydberg Equation for hydrogen spectrum
1 / λ = RZ2 [1/n12 – 1/n22]
● Bohr’s model for one electron systems:
1. Mvr = nh/2π
2. En (energy of transition) = -(E1/n2)Z2 = -13.6 Z2/n2 eV; E1 = -2π2me4 / n2
3. En (energy of ionization) = +(E1/n2)Z2 = +13.6 Z2/n2 eV
4. rn = n2/Z * n2/4π2e2m = 0.529 * n2 / Z A
5. v = 2πZe2 / nh = (2.18 * 106 * Z/n) m/s
6. period of evolution of e- in nth orbit; Tn = 2πr/Vn – (n3/Z2 x 1.5 x 10-16) sec.
● Debroglie wavelength: λ = h/mc = h/p
● Heisenberg’s uncertainity principle: ∆n ∆p ≥ h/4π or ∆n ∆v ≥ h/4πm

59
 Atomic structure

Exercise-I
IAT Based Problem

1. What possibly can be the ratio of the de Broglie wavelength for two electrons having the same initial
energy and accelerated through 50 and 200 volts?

A. 3:10
B. 10:3
C. 1:2
D. 2:1

2. If λ 0 is the threshold wavelength for photoelectric emission, l wavelength of light falling on the
surface of metal, and m mass of electron, then de Broglie wavelength of emitted electron is

ℎ(λ λ0)
A. [ 2𝑚𝑐(λ0− λ ) ]1/2
ℎ(λ0−λ )
B. [ 2𝑚𝑐(λ0λ ) ]1/2
ℎ(λ−λ0)
C. [ 2𝑚𝑐(λλ0 ) ]1/2
ℎ(λ λ0) 1/2
D. [ 2𝑚𝑐
]

3. It is known that atoms contain protons, neutrons and electrons. If the mass of neutron is assumed to
half of its original value whereas that of proton is assumed to be twice of its original value then the
atomic mass of 146 C will be

A. Same
B. 25 % more
C. 14.28 % more
D. 28.5 % less

4. The shortest wavelength of He+ in Balmer series is x. Then longest wavelength in the Paschene
series of Li2+ is

A. 36x/5
B. 16x/7
C. 9x/5
D. 5x/9

5. An electron in a hydrogen atom in its ground state absorbs energy equal to ionisation energy of Li+2.
The wavelength of the emitted electron is

A. 3.32 x 10-10 m
B. 1.17 A0
C. 2.32 x 10-9 nm
D. 3.33 pm

6. If the nitrogen atom had electronic configuration 1s7, it would have energy lower than that of normal
ground state configuration 1s2 2s2 2p3, because the electrons would be closer to the nucleus. Yet
1 s7 is not observed because it violates

60
 Atomic structure

A. Heisenberg uncertainty principle

B. Hund’s rule
C. Pauli’s exclusion principle
D. Bohr postulate of stationary orbits

7. Two bulbs A and B are emitting monochromatic light of wavelength such that A can just ionise H
atoms and B can just ionise He+ ions. If the power of A and B are 30 W and 40 W respectively,
calculate the ratio of number of photons emitted per second by bulb A to bulb B.

A. 4:1
B. 5:1
C. 3:1
D. 7:1

8. The ratio of difference in wavelengths of first and second lines of Lyman series in H-like atom to
difference in wavelength for second and third lines of same series is

A. 2.5:1
B. 3.5:1
C. 4.5:1
D. 5.5:1

9. Which of the following statements is INCORRECT?

𝑒
A. 𝑚
ratio for canal rays is maximum for hydrogen ion.
𝑒
B. 𝑚
ration for cathode rays is independent of the gas taken.
C. The natural of canal rays is dependent on the electrode material.
2
𝑒 𝐸
D. The 𝑚
ratio for electron is expressed as 2 , when the cathode rays go undeflected under the
2𝐵 𝑉
influence of electric field (E), magnetic field(B) and V is potential difference applied across
electrodes.

10. The quantum numbers of four electrons (e1 to e4) are given below.

n l m s
e1 3 0 0 +1/2
e2 4 0 1 1/2
e3 3 2 2 –1/2
e4 3 1 –1 ½

The correct order of decreasing energy of these electrons is

A. e1 > e3 > e2 > e1

B. e2 > e3 > e4 > e1
C. e3 > e2 > e4 > e1
D. none

61
 Atomic structure

11. In a sample of hydrogen atoms, electrons jump from 10th excited state to ground state. If x is the
number of different ultraviolet radiations, y is the number of different visible radiations and z is the
number of different infrared radiations. The value of z – (x + y) is

[Assume all the Balmer lines lie within visible region.]

A. 17
B. 18
C. 19
D. 36

12. The ratio of the wavelength of a proton and a-particle will be 1 : 2 if their

A. velocity of proton to velocity of a particle is in the ratio 1 : 8.

B. velocity of proton to velocity of a particle is in the ratio 8 : 1.
C. kinetic energy of proton to kinetic energy of a particle is in the ratio 64 : 1.
D. kinetic energy of proton to kinetic energy of a particle is in the ratio 6 : 1.

13. The electrons, identified by quantum numbers n and l, (i) n = 4, l = 1, (ii) n = 4, l = 0, (iii) n = 3, l =
2, and (iv) n = 3, l = 1 can be placed in order of increasing energy, from the lowest to highest, as

A. (iv) < (ii) < (iii) < (i)

B. (ii) < (iv) < (i) < (iii)
C. (i) < (iii) < (ii) < (iv)
D. (iii) < (i) < (iv) < (ii)

14. The work function for a metal is 4 eV. To emit a photo electron of zero velocity from the surface of
the metal, the wavelength of incident light will be

A. 2700 Å
B. 1700 Å
C. 5900 Å
D. 3100 Å

15. If λ1 and λ2 denote the de Broglie wavelength of two particles with same masses but charges in the
ratio of 1: 2 after they are accelerated from rest through the same potential difference, then

A. λ1= λ2
B. λ1 < λ2
C. λ1 > λ2
D. None of these

13.6
16. The energy for an electron is an orbit of hydrogen atom is given by, En = - 2 Z2 eV. Calculate the
𝑛
energy of the orbit having a radius 9r1 where r1 is the radius of the first orbit?

A. -1.51 eV C. 13.6 eV
B. 10.2 eV D. 1.36 eV

62
 Atomic structure

17. An electron in a Bohr orbit of hydrogen atom with the quantum number n2 has an angular
momentum 4.2176 x 10-34 kg m2 s–1. If electron drops from this level to the next lower level, find the
wavelength of this line.

A. 18.75 * 10-7 m
B. 1.87 * 10-7 m
C. 187.5 * 10-7 m
D. 0.187 * 10-7 m
----------------------------------------------------------------------------------------------------------------------------
NEST Based Problems

1. What is likely to be principal quantum number for a circular orbit of diameter 20 nm of the hydrogen
atom if we assume Bohr orbit be the same as that represented by the principal quantum number?

A. 10
B. 14
C. 12
D. 16

2. Consider the following nuclear reactions involving X and Y:

X → Y + 2He4
Y → 8O18 + 1H1

If both neutrons as well as protons in both sides are conserved in nuclear reaction then identify
period number of X and moles of neutrons in 4.6 g of X.

A. 3, 2.4
B. 3, 1.4
C. 2, 4.6
D. 3, 0.2

3. Electromagnetic radiations having λ = 310 Å are subjected to a metal sheet having work function =
12.8 eV. What will be the velocity of photoelectrons with maximum kinetic energy?

A. 0, no emission will occur

B. 2.18 x 106 m/s
C. 2.18 2 x 106 m/s
D. 8.72 x 106 m/s

4. Match the following:

(a) Energy of ground state of He+ (i) –6.04 eV

(b) Potential energy of I orbit of H-atom (ii) –27.2 eV
(c) Kinetic energy of II excited state of He+ (iii) 8.7 X 10–18 J
(d) Ionisation potential of He+ (iv) –54.4 eV

A. a – (i), b – (ii), c – (iii), d – (iv)

B. a – (iv), b – (iii), c – (ii), d – (i)

63
 Atomic structure

C. a – (iv), b – (ii), c – (i), d – (iii)

D. a – (ii), b – (iii), c – (i), d – (iv)

5. Give the correct order of initials True (T) or False (F)for the following statements:

(I) Number of electrons having ‘l = 0’ is 10 in Pd.

(II) The value of Zeff for 3d electron of Cr and 3d electron of Mn is same as the number of
electron in ‘d’ subshell of Cr and Mn are same.
(III) Multiplicity of Fe is equal to Ni+2.
𝑙
(IV) Value of ( 𝑛 ) for last electron of element having atomic number 57 is 0.4.

A. TTTT
B. FTTT
C. TFTF
D. FFFT

6. The electrons in a sample of gaseous Li2+ ions which are initially present in a particular excited state
makes a transition to a lower level. The emitted photons are absorbed by a sample of H-atoms which
are present in their ground state. This sample of H-atoms on deexcitation gives maximum 6 different
types of spectral lines. Find the quantum number of initial excited state of Li2+ ions.

A. 11
B. 12
C. 13
D. 14

2
7. The radial wave function for 1s electron in H-atom is R = 3 e-r/a0 where a0 = radius of first orbit of
𝑎0 2
H-atom. The ratio of probability of 1s electron in hydrogen atom at distance a0 from nucleus to that at
𝑎0
distance 2 from nucleus is

A. Equal
B. 1/e times
C. 4/e times
D. e/4 times

8. When photons of wavelength λ = 253.7 nm is subjected on Cu plate (work function = 4.65 eV) then
photoelectrons are emitted. The magnitude of potential required to stop photocurrent completely is 0.24
V. The kinetic energy of ejected electron is

(I) 0.24 eV (II) 0.20 eV

(III) 0.10 eV (IV) 2.4 eV

A. I, II, III
B. II, III, IV
C. I, III, IV
D. All of these

9. Consider an electron in the nth orbit of a hydrogen atom in the Bohr model. The circumference of the
orbit can be expressed in terms of the de Broglie wavelength λ of the electron as

64
 Atomic structure

A. 0.529 n λ
B. 𝑛 λ
C. 13.6 λ
D. n λ

10. A particle X moving with a certain velocity has a de Broglie wavelength of 1 Å. If particle Y has a
mass of 25% that of X and velocity 75% that of X, de Broglie’s wavelength of Y will be

A. 3Å
B. 5.33 Å
C. 6.88 Å
D. 48 Å

11. The energies of energy levels A, B and C for a given atom are in the sequence EA < EB < EC. If the
radiations of wavelengths λ1, λ2 and λ3 are emitted due to the atomic transitions C to B, B to A and C to
A respectively then which of the following relations is correct?

A. λ1 + λ2 + λ3 = 0
B. λ3 = λ1 + λ2
C. λ2 = λ3 + λ1
λ1λ1
D. λ1 = λ1+ λ1

12. Let ν1 be the frequency of the series limit of the Lyman series, ν2 be the frequency of the first line of the
Lyman series, and ν3 be the frequency of the series limit of the Balmer series.

A. ν1 – ν2 = ν3
B. ν2 – ν1 = ν3
C. ν3 = 1/2 (ν1 – ν3)
D. ν1 + ν2 = ν3

13. In Bohr’s model of the hydrogen atom, the ratio between the period of revolution of an electron in the
orbit of n = 1 to the period of the revolution of the electron in the orbit n = 2 is

A. 1:2
B. 2:1
C. 1:4
D. 1:8

ASSERSION AND REASON: Statement I (assertion) and Statement II (reason). And options are:

A. Statement I is true, Statement II is true Statement II is the correct explanation for Statement I.
B. Statement I is true, Statement II is true Statement II is NOT a correct explanation for statement I
C. Statement I is true, Statement II is false.
D. Statement I is false, Statement II is true.

14. Statement I: Nodal plane of px atomic orbital in yz plane.

Statement II: In px, atomic orbital electron density is zero in the yz plane.

65
 Atomic structure

15. Statement I: Cu+ is repelled by magnetic field.

Statement II: All electrons are paired up in Cu+ ion.

16. Statement I: No two electrons in an atom can have the same values of four quantum numbers.
Statement II: No two electrons in an atom can be simultaneously in the same shell, same subshell,
same orbitals and have the same spin.

17. Statement I: p-orbital has dumb-bell shape. Because

Statement II: Electrons present in p-orbital can have one of three values for ‘m’, i.e., 0, +1, –1

18. Statement I: The ground state configuration of Cr is 3d5 4s1.

Statement II: A set of exactly half-filled orbitals containing parallel spin arrangement provide extra
stability.

19. Statement I: Mass numbers of the elements may be fractional.

Statement II: Mass numbers are obtained by the sum of mass of electron and neutron.

20. Alpha particles capture free moving electrons having wavelength 0.25 nm and form excited H-like
species. In this excited state, electron has circumference 6 times the wavelength of electron. Bohr’s
quantisation rule is applicable. The energy of photon emitted in this process will be

A. 20.49 eV
B. 22.49 eV
C. 25.51 eV
D. 27.51 eV

21. The effective nuclear charge (Zeff) considers the interelectronic repulsion in multielectron atoms.
Slater’s rule helps us in evaluating Zeff for various species. Apply Slater’s rules to answer the following
questions.

Zeff for 3d electron of Zn = x

Zeff for 3d electron of Zn2+ = y
Zeff for 4s electron Zn = z
Choose the correct option(s):

A. x>z
B. y>z
C. x=y
D. All of these

22. Consider a hypothetical atom where, px, py, pz and dxy, dxz , dyz dx2-y2 orbitals are present for principal
quantum number n = 3. Which of the following orbital’s lobe is not present at all either in the nodal
plane of px orbital or in the nodal plane of py orbital?

A. dxy
B. dx2-y2
C. dyz
D. pz

66
 Atomic structure

23. Three quantum numbers are required to define an orbital while four quantum numbers are required to
describe an electron. (n + l) is maximum and minimum for which orbitals are 6s, 5p, 6d, 4d, 2p, 3s, 2s?

A. 6f and 1s
B. 6d and 2s
C. 5p and 3s
D. 6s and 2p

24. Which of the following statements is incorrect?

A. In calculation of s value (shielding constant) for an electron in 4s orbital, the contribution of 1s

electron is 0.3.
B. In calculation of s value for of an electron in 3d orbital, the contribution of 4s electron is zero.
C. In calculation of s value for an electron in 3d orbital, the contribution of electron present in 3p
orbital is 1.0.
D. In calculation of s value for an electron in 4s orbital, the contribution of electron present in 3p
orbital is 0.85.

25. Nodal plane of an orbital is the region around the nucleus where probability of finding electrons of that
orbital is zero. Number of nodal planes of an orbital = l. Which of the following contains at least one
common nodal plane?

A. px and dxz
B. dxz and dx2-y2
C. dx2-y2 and dz2
D. pz and dz2

26. A hydrogen - like atom has ground state binding energy 122.4 eV. Then

A. its atomic number is 3.

B. an electron of 90 eV can excite it to a higher state.
C. an 80eV electron cannot excite it to a higher state.
D. an electron of 8.2 eV and a photon of 91.8 eV are emitted when a 100eV electron interacts with
it.

27. Energy equivalent of 10.00 cm–1 is

A. 2 x 10-22 J per photon

B. 2.9 x 10-2 kcal mol–1 photon
C. 1.2 x 10-1 kJ mol–1 photon
D. 2 x 10-15 ergs per photon

28. Radiation of wavelength 200 Å falls on a platinum surface. If the work function of the metal is 5 eV,
which of the following results are correct about experiment?

A. The velocity of photoelectrons increases with increase in intensity of radiation.

B. Photo-emission of electrons takes place.
C. The threshold frequency of the metal is 1.21 x 1015 sec–1.
D. The velocity of the photo-electrons is 4.48 x 106 m/sec.

67
 Atomic structure

Exercise II
IAT PYQ’s

1. How many radial nodes does Ca+ have in its 4s orbital?

[IAT 2023]
A. 3
B. 0
C. 1
D. 2

2. The probility density of an electron in 1s orbital for an H atom is maximum

[IAT 2021]
A. at infinite distance.
B. at the Bohr radius.
C. at twice the Bohr radius.
D. at the nucleus.

3. The total number of nodes for a given principal quantum number n, and azimuthal quantum number l,
are
[IAT 2019]
A. sum of l angular nodes and n+l-1 radial nodes.
B. sum of l angular nodes and n-l-1 radial nodes.
C. sum of l+1 angular nodes and n-l-1 radial nodes.
D. sum of l+1 angular nodes and n+l-1 radial nodes

NEST PYQ’s

1. Consider a hypothetical one-electron atom, where the nucleus and the electron interact with a force 𝐹 =
−𝑘𝑟. Here, 𝑟 is the distance between the electron and the nucleus, and 𝑘 is a constant. If this atom is
studied using the Bohr model, the electron is assumed to move around the nucleus in selected stable
orbits of fixed radii, characterized by quantum number 𝑛. The radius of the orbiting electron (of mass
𝑚e) is

[ NEST 2023 ]

1/4

A. ( 2 2
𝑛ℎ
2
4π 𝐾𝑚𝑒 )
B. ( 2 2
𝑛ℎ
2
4π 𝐾𝑚𝑒 ) 1/3

C. ( 2 2
𝑛ℎ
2
4π 𝐾𝑚𝑒 ) 1/2

D. ( 2 2
𝑛ℎ
2
4π 𝐾𝑚𝑒 )
68
 Atomic structure

2. The ground state electronic energy of He atom (EHe) can be expressed in terms of the ground state
energy of the hydrogen atom ( EH ) and the electron-electron interaction energy (Eee) in the He atom. If
Eee is equal to x times the magnitude of EH, then EHe is given by:

[ NEST 2023 ]

A. EHe = 4 EH + xEH
B. EHe = 2(4 EH + xEH)
C. EHe = 8 EH – xEH
D. EHe = 8 EH + xEH

3. Among the following, the correct statement is

[ NEST 2022 ]

2
A. For denoting the normalized wavefunction of a one- electron system, the value of | \ at any point r
2
cannot exceed one since the integral of | \ over the whole space is one
B. The ionization potential of He atom is greater than that of He+ ion
C. If the ionization potential of the hydrogen atom is 13.6 eV, the first excited state of He+ ion will be
13.6 eV.
D. According to the prediction of simple molecular orbital theory, the bond orders of He2+ ion and H2+
ion are the same

4. The correct order of the wavelengths of the radiations, associated with the following
[NEST 2021]
A. red-light from traffic signal < sodium D-lines<stretching vibration of H₂O < transmission from
FM radio.
B. transmission from FM radio<stretching vibration of H₂O < sodium D lines < red-light from
traffic signal.
C. sodium D-lines < red-light from traffic signal stretching vibration of H2O < transmission from
FM radio.
D. sodium D-lines < stretching vibration of H₂O < red-light from traffic signal

5. Let the ground state electronic energy of hydrogen atom be EH eV. The first excited state energy of
deuterium atom (in eV) is
[NEST 2021]
A. EH/4
B. EH/2
C. lower than ЕH/4
D. higher than EH/4

69
 Atomic structure

6. For a hydrogenic quantum system, the probability of finding the election Dnl(r)dr in a spherical shell of
radius r (with nucleus at its center) and thickness dr, is plotted against r (in units of in a0 ) for three sets
of values of n and I (plots I, II, and III). The principal quantum number (n), azimuthal quantum number
(l) and are under the curve (A) corresponding to the three plots are denoted by subscripts I, II and III
respectively. (The plots are not drawn to scale.) The correct statement(s)

[NEST 2020]
A. lI > lII> lIII
B. Energy of the system corresponding to each plot depends on the respective l value.
C. AI = AII = AIII
D. lI + lII + lIII ≥ 3

7. The correct order of ionic radius is:

[NEST 2020]
+ 2+ - 2- 3-
A. Na < Mg < F < O < N
B. Mg2+<Na+ <F <O²- <N³-
C. F-<O²-<N³-<Na+<Mg²+
D. N³- <O2-< F- < Na+ <Mg²+

8. The Lyman series corresponds to the emission lines of hydrogen atom due to the transitions of the type
n → 1 (2 → 1, 3 → 1, 4 → 1, etc) where is the principal quantum number of the excited state. The
ionization energy of the hydrogen atom can be determined by plotting
[NEST 2020]
A. Frequency differences between successive emission lines vs emission frequencies
B. Emission frequency vs n²
C. Emission frequency vs 1/n²
D. Frequency differences between successive emission lines vs n

9. In H atom, the electron is bound by Coulomb interaction and its three quantum numbers n, l, m are
related as n= 1, 2, 3, 4....; l = 0, 1, 2....n-1; m = -l, -(l-1)…...0…, (l-1), l. The spin quantum number s=
1/2 and -1/2. Thus, the maximum number of electrons occupying the first four shells (n = 1, 2, 3, 4) are
2, 8, 18, 32. respectively. In artificial atoms (atomic clusters), where the electrons are bound by
spherical harmonic oscillator potential, n= 0,1, 2, 3, 4.... with l = 0, 2, 4, 6…. n, for even n, and l =1, 3,
5, 7.... n for odd n. The possible values of m and s remain the same as in the case of H atom. The filled
shell configuration for this system for filling up to n = 1, 2, 3 and 4 will respectively correspond to the
electron numbers.
[NEST 2019]
A. 18, 20, 40, 70
B. 6, 18, 38, 68
C. 6, 12, 20, 30
D. 2, 8, 18, 32

10. The energy of an electron in the 1s orbital of H−, He, Li+ and Be2+ follows the order
[NEST 2019]

70
 Atomic structure

A. H− > He > Li+ > Be2+

B. Li+ > Be2+ > He > H−
C. Be2+ > Li+ > He > H−
D. H− > Li+ > He > Be2+

11. The plot of 𝝌-1 vs T (𝝌 = molar magnetic susceptibility, T = absolute temperature) for a paramagnetic
compound that follows Curie equation is
[NEST 2014]

A. B.

C. D.

12. Assume that Pauli's exclusion principle can permit three electrons per orbital rather than two. The
correct statement(s):
[NEST 2014]
A. 9 electrons are needed in the outermost shell for a noble gas configuration.
B. 3 electrons would be shared in a covalent bond.
C. The electron dot structure of an element X with Z = 12 is:
D. Assuming MO diagram of N2 is valid for X₂ (Z = 12), the bond order of X₂ is 2.

13. The probability distribution for the speed (v) of molecules for an ideal gas at temperature T, is given by
2
𝑚 𝑚𝑣
f(v) = 4v2 ( 2π𝑇𝐾 )3/2 exp (− 2𝑇𝐾𝐵
)
𝐵

Where m is the mass of a molecule and kB is the Boltzmann constant. Among the following, the
correct statement is
[NEST 2012]
2/3
A. The most probable velocity is proportional to T .
B. For two different gases A and B, the average velocity of the molecules of A in same as that of B,
at a given temperature.

71
 Atomic structure

C. For two different gases A and B. the average kinetic energy of the molecules of A is same as that
of B, at a given temperature.
D. The most probable velocity is higher than the average velocity.

14. The electron in H atom-like species makes a transition from an excited state to the ground state. In this
process, its
[NEST 2010]
A. kinetic and total energies decrease but potential energy increases.
B. kinetic energy decreases whereas the potential and total energies remain the same.
C. kinetic energy increases but potential and total energies decrease.
D. kinetic, potential and total energies decrease.

15. In the nuclear reaction

23
Na11+X → Y+1n0
X and Y are
[NEST 2011]
1 23
A. H1 and Mg12
4
B. He2 and 27Al13
3
C. H1 and 24Mg12
2
D. H1 and 23Mg12

16. The metal ion whose hydrated form will be almost colourless is
[NEST 2009]
+
A. Cu²
B. Na2+
C. Mn²+
D. Co²+

17. Given below are electronic configurations of some atoms/ions. Which of these represent excited states?
(Atomic numbers: C = 6, Cr = 24, Na = 11 and Si = 14)
[NEST 2008]
2 2 6 2 6 5 1
A. Cr: 1s 2s 2p 3s 3p 3d 4s
B. Na+: 1s2 2s2 2p5 3p1
C. Si: 1s2 2s2 2p6 3s2 3p2
D. C: 1s2 2s1 2p3

72
 Atomic structure

Answer Key:
Exercise I
IAT Based Problems

1 D 6 C 11 A 16 A

2 A 7 C 12 B 17 A

3 C 8 B 13 A

4 B 9 C 14 D

5 B 10 C 15 C

NEST Based Problems

1 B 8 A 15 A 22 A

2 A 9 D 16 D 23 B

3 C 10 B 17 B 24 A

4 C 11 D 18 A 25 A

5 D 12 A 19 B 26 A, B, C

6 B 13 D 20 C 27 A, B, C, D

7 C 14 B 21 D 28 B, C, D

Exercise: II
IAT PYQ’s

1. A 2. B 3. B

NEST PYQ’s

1 A 6 A,B,C,D 11 A 16 A

2 C 7 B 12 B, D 17 B, D

3 D 8 A 13 C

4 C 9 A 14 C

5 C 10 A 15 A

73
 Atomic structure

74