Dr.

Piyali Paul
Department of Chemistry
Heritage Institute of Technology
Kolkata-700 107
 Atomic structure history timeline
Democritus , a Greek philosopher, was the first man who
proposed that matter is made up of particles. He named
these particles, ‘atomos’ meaning indivisible. This was the
Democritus’ Atomic Theory. Due to the lack of technological
Democritus setup back then, scientists had very limited information on
400 B.C. this theory.

Almost after two thousand years, the works on

the simplifying matter was materialized by scientist, John
Dalton. In 1808, John Dalton postulated the famous
Dalton’s Atomic Theory. the postulates of this theory are
given below.
John Dalton
• All matter consists of indivisible particles called atoms.
1808
• Atoms of the same element are similar in shape and mass,
but differ from the atoms of other elements.
• Atoms cannot be created or destroyed.
• Atoms of different elements may combine with each other in
a fixed, simple, whole number ratios to form compound atoms.
• Atoms of same element can combine in more than one ratio
to form two or more compounds.
• The atom is the smallest unit of matter that can take part
in a chemical reaction.
 Thomson used a cathode ray discharge tube is his experiment
to deduce the presence of a negatively charged particle i.e.
electron. He used several types of metals in the form of
electrode materials and found out that the properties
remained constant. This proved and concluded a few things
such as:
J.J. Thomson
• The beam of particles or cathode rays has negatively
1897 charged particles and these negatively charged particles are
Discovery of the electrons.
electron • The electrons are necessary constituents of all atoms.
• We can find the subatomic particles (electrons) within atoms
He got Nobel of all kinds of elements.
Prize on 1900 This model consists of a sphere
J.J. Thomson’s filled with positive charge cloud
atomic model where the negative charges are
embedded.
(10-3 mm of Hg)
Plum-pudding model or Watermelon model

(100000V)
 German scientist Eugene Goldstein used a discharge tube filled
with hydrogen gas in his Canal Ray Experiment for the
discovery of proton (positive particles). The discovery of
proton which happened along with the discovery of the
electron further strengthened the structure of the atom. In
this experiment, Goldstein applied high voltage across a
discharge tube which had a perforated cathode. A faint
Eugen Goldstein
luminous ray was seen extending from the holes in the back of
1886 the cathode. • Unlike cathode rays, canal rays or
anode rays depend upon the nature
Discovery of proton
of gas present in the tube. It is
because the anode rays are
composed of positive ionized ions
formed by ionization of gas present
in the tube.
• The charge to mass ratio (e/m) for
the particles of the ray was found
to be different for different gases.
• The behaviour of particles in an
electric and magnetic field was
opposite to that of cathode rays.
• Some positively charged particles
carry multiples of the fundamental
value of the charge.
 Ernest Rutherford, a British scientist, conducted Alpha particle
scattering experiment by bombarding a thin sheet of gold (100 nm
thickness) with α-particles and then he studied the trajectory of these
particles after their interaction with the gold foil and in order to study
the deflection caused to the α-particles, he placed a fluorescent zinc
sulphide screen around the thin gold foil. After this experiment,
Rutherford made certain observations based on which he explained the
atomic structure of elements and proposed Rutherford’s Atomic Model
Ernest Rutherford which contradicted Thomson’s atomic model.
(1911)

Observations
After the bombardment α-particles with gold sheet
• A major fraction passed through the sheet without any deflection.
• Some of the α-particles were deflected by the gold sheet by very small angles,
• Very few were deflected back (only a few α-particles had nearly 180o deflection
angle.
 Based on the findings of alpha particle scattering experiment, Rutherford proposed
the atomic structure of elements. According to the Rutherford atomic model:
 The positive charge and most of the mass of an atom is concentrated in an
extremely small volume. He called this central region of the atom as a nucleus.
 Rutherford’s model proposed that the negatively charged electrons surround the
nucleus of an atom. He also claimed that the electrons surrounding the nucleus
revolve around it with very high speed in circular paths. He named these circular
paths as orbits.
 Electrons being negatively charged and nucleus being a densely concentrated mass
of positively charged particles are held together by a strong electrostatic force of
attraction.

Limitations
According to Maxwell, Hence an electron being negatively charged and
1 accelerated charged particles it is also revolving around the nucleus should
emit electromagnetic radiations emit electromagnetic radiation (energy).

Rutherford model could not explain

the stability of an atom. Electrons would collapse in the nucleus

stability of an atom X
2 Rutherford was also unable to explain the line spectrum of hydrogen atom.
 Niels Bohr
1913
Postulates of Bohr's atomic model
 Bohr proposed that in an atom electron is revolving around the nucleus in a definite,
circular path called orbits or shells.
 These orbits are called ‘stationary orbits’ and each orbit or shell possesses fixed
radius and fixed energy.
 The electron revolves only in those orbital for which the orbital angular momentum is
integral multiple of (h/2π); where h is the Planck's constant (6.626x10-34 Js).
 The energy levels are represented by an integer called quantum numbers where n =
1,2,3,..... These integers n = 1,2,3,....indicate principal quantum numbers i.e. orbits
that can be assigned as K, L, M & N. Thus, the electron in the lower energy state is
called the ground state.
 The change in energy will occur when the electron jumps from one orbit to another
orbit.
 The electron gains energy (energy absorption) when it jumps from a lower energy
level to a higher energy level and the electron loses its energy (energy emission) as it
jumps from the higher energy to a lower energy level. DE = E2-E1 = hn
Radii of the Bohr’s stationary orbits
In Bohr theory, the basic Rutherford model is maintained; only an extra restriction
regarding angular momentum is introduced means electron revolves only in those orbital
for which the orbital angular momentum is integral multiple of (h/2π). Hence, the
condition of equilibrium between centrifugal force and coulombic force still applies to
these orbit. Let's consider an electron with mass m is moving in an orbit of radius r
with speed v around the nucleus with Z unit of positive charge.
εon2h2
r =
pmZe2
for H-atom (Z=1)

The radius of the smallest

possible orbit in H-atom is
5.293 X 10-11 m or 0.05293 nm

This is the radius of 1st

Bohr orbit (denoted by ao)

Hydrogen like atoms: He+

(Z=2), Li2+ (Z=3), Be3+ (Z=4)
with a single electron.
 Energy of an electron in a Bohr’s orbits
An electron in the atom possesses (i) kinetic energy by virtue of its motion and (ii)
potential energy due to its attachment to the nucleus. The total energy is sum
of these two energy terms. The two energy terms will be calculated separately.
Kinetic energy
We know, kinetic energy for a particle of mass m and velocity v is given by the
expression . For an electron in an orbit of radius r, we have the additional
relation

Ze2
Thus, kinetic energy of the electron =
8pεor
Potential energy
The potential energy of an electron in an atom is calculated with reference to its
position at infinity from the nucleus; at this point the potential energy is assigned
zero value. The potential energy is then given by the total work done in bringing the
electron from infinity to its position in the orbit of radius r. The force involved is
the coulombic force of attraction by the nucleus, Ze2/4pεor2.
r=r
Ze2 Ze2
The work done and hence the potential energy = = -
4pεor2 4pεor
r=∞
The negative sign implies that work has to be done to remove the electron away from
the nucleus.
Total energy of the electron: Since the total energy (E) of the electron is the sum of
its kinetic energy and potential energy, we may write
To remove electron
Ze2 Ze2 Ze2 need to supply that
E =
8pεor
- 4pεor
=-
8pεor
amount of energy

Z2me4 Z2 putting the values

Putting the expression for r, we get E = - 8ε 2n2h2
= -13.6
n2
eV for m, e, εo, and h
o

-13.6
For hydrogen atom the amount of energy (E) = eV
n2
Considering hydrogen atom,
For ground state (n=1), the energy (En=1) = -13.6 eV

Minimum amount of energy for electron

For 1st excited state (n=2), the energy (En=1) = -3.4 eV
For 2nd excited state (n=3), the energy (En=1) = -1.5 eV
For 3rd excited state (n=4), the energy (En=1) = -0.85 eV=-0.9 eV

-13.6
Ionization energy (En=a) = eV = 0 eV
a2

Maximum amount of
energy for electron
 Energy absorption and Energy emission by an Electron
The electrons within an atom jump The electrons within an atom jump
from lower atomic energy level to from higher atomic energy level to
a higher energy level a lower energy level

Energy (in form of light) is absorbed Energy (in form of light) is emitted
This is called This is called
Energy Absorption Energy Emission

The spectrum generated due to The spectrum generated due to Emission

transition of electron from lower transition of electron from higher Line Spectra
to higher energy levels by the to lower energy levels by the for H-atom
absorption of energy is known as emission of energy is known as has been
ABSORPTION SPECTRA EMISSION SPECTRA described
here

Continuous spectra Line spectra

When the spectrum has no breaks or gaps When atoms are excited they emit light of certain
between the wavelength range is known as wavelengths which correspond to different colors. The
a continuous spectrum. That means it emitted light can be observed as a series of colored
includes a spectrum of all wavelengths of lines with dark spaces in between; this series of
light or in other words, it is a spectrum colored lines is called a line or atomic spectra. Each
that contains all colors. element produces a unique set of spectral lines.
Emission Line Spectra for H-atom evidence to show the quantized
electronic structure of an atom
hydrogen electrons in hydrogen
An electric
molecule hydrogen atoms are means atoms are energetically
discharge is
dissociate into energetically excited (from lower to
passed through a
hydrogen excited by higher energy levels)
gaseous hydrogen
atoms absorption of energy
molecule

Then excited electron jump

from higher to lower energy

It results in
the emission of
electromagnetic
radiation

This is emission
spectrum

This emission spectrum of

hydrogen atom consist of
DE radiations of discrete
frequencies/discrete energies.

٧ = frequency of emitted radiation

l=
frequency of emitted radiation
٧ = wave number of emitted radiation
DE =
 DE =

c Z2me4
or, h =
l 8εo2h2

or, ٧ =

On the basis of the values n1 and n2

(present in above equations) the
hydrogen emission spectrum is
obtained with different wavelength.
These spectrum is the combination
of series of lines in different region
of electromagnetic radiation.

Lyman, Balmer, Paschen,

Brackett, Pfund

Five series of spectral

lines in different region of
electromagnetic radiation
Calculate the wavelength of spectral lines when an electron drops from the third to
the second Bohr orbit in a hydrogen atom. (RH=1.09678×107 m-1). In which region of
electromagnetic spectrum does this radiation fall?

n1= 2 n2= 3 Z= 1 (for hydrogen atom)

RH=1.09678×107m-1

[ ] [ ]
= 1.09678×107×1 1/22-1/32 = 1.09678×107×1 1/4-1/9 = 1.09678×107×1 1/4-1/9[ ]
In visible region of electromagnetic BALMER
= 6.566×10-7m = 6566 Å
spectrum does this radiation fall series

Calculate the wavelength of emitted light for the transition of energy level n=4 to
energy level n=1 for the hydrogen electron transition. In which region of
electromagnetic spectrum does this radiation fall? (RH = 1.096776x107 m-1 )
n1= 1 n2= 4 Z= 1 (for hydrogen atom)

[
= 1.09678×107×1 1-1/42 ] = 1.09678×10 ×1×15/16]
7

= 0.9728×10-7m = 973Å In UV region of electromagnetic Lyman

spectrum does this radiation fall series
 Max Planck's quantum theory
According to Planck’s quantum theory,
 Different atoms and molecules can emit or absorb energy in discrete quantities
only. The smallest amount of energy that can be emitted or absorbed in the form of
electromagnetic radiation is known as quantum.
 The energy of the radiation absorbed or emitted is directly proportional to the
frequency of the radiation.
Wave like property Light
(previously established)
Dual nature According to Planck Light wave is
of Light composed of tiny
packets of energy
particle like
Quanta
property of light
Max Planck or
Photon
The energy of radiation is expressed in terms of frequency as,
E = h ν = hc/l Fixed energy
Where, E = Energy of the radiation
h = Planck’s constant (6.626×10–34 Js) Fixed wavelength
ν= Frequency of radiation, l= Wavelength of radiation

Calculate the energy per photon for radiation of wavelength 650 pm.
(Given h = 6.625X10-34 J.s and c = 3X108m/s)
650 pm = 650X10-12m
6.625X10-34X3X108 = 6.5X10-10m
E = hc/l = = 3.06X10-16 J
6.5X10-10
 de Broglie hypothesis
Guided by the dual nature of radiation (light) de Broglie conceived a
similar dual character for matter in 1924 .
atom
particle like nature
Electron
dual character Louis de Broglie
wave like nature Why?
According to de Broglie an electron When a tiny particle
bound to the nucleus behave like a like electron
standing or stationary wave (m=9.11X10-31kg)
standing or stationary wave.
(a wave which don’t travel) moving around the
nucleus with velocity
Now if a microscopic particle like electron of mass m moving with a (v=nh/2pmr) shows
speed of light c, then from mass energy relation of Einstein its the wave like
energy E= mc2, and from Planck’s equation the photon energy E= hν, feature.
So comparing E=mc2 and E=hν h = Planck’s constant
or, mc2 = hν = hc/l
or, mc = h/l
p= momentum of electron
l= de Broglie wavelength l=h/p
or, l= h/mc=h/p=Planck’s constant/momentum
According to de Broglie, “a microscopic particle
in motion is also associated with waves”.
Shortly afterwards, a diffraction pattern was obtained with a beam of electron
striking a nickel crystal (Davisson & German; 1927); the pattern was very similar in
appearance to diffraction patterns obtained with electromagnetic waves, e.g., X-rays.
This similar observations characteristics of wave nature of electrons.
 Significance of de Broglie’s equation
The de Broglie’s equation is applicable for all particles but wave aspect is
of significance only with tiny/microscopic particle like electrons.
Large mass: Suppose a cricket ball Tiny/microscopic mass: Let us consider
of mass 200g (0.2kg) is moving a an electron mass 9.11x10-31kg moving
speed of 100m/s then with a speed of 6 x 106m/s then
6.625x10-34
6.625x10-34 l= h/mc=
l= h/mc= 9.11x10-31x6x106
0.2x100
= 1.21 x 10-10 m
= 3.3125x10-35 m

wavelength is
wavelength is too measurable
small to measure
Significant wave
wave property very property
less significant
Prominent wave property for
No wave property for large mass tiny/microscopic mass
Broglie’s relation has no significance in everyday life, since in everyday life
we come across macroscopic objects.
Consider a beam of electron with speed 5.31X106 m/s. Calculate the de
Broglie wavelength. (Mass of electron = 9.11X10-31 kg; h=6.626×10−34Js).

According to de Broglie hypothesis,

l= h/mc = 6.626×10−34/(9.11X10-31X5.31X106)
= 0.13697X10-9 m
= 1.3697X10-10 m
= 1.3697 Å
 This principle is based on the
Heisenberg Uncertainty Principle wave-particle duality of matter.
Heisenberg’s uncertainty principle states that it is impossible to determine
simultaneously, the exact position and the exact momentum (or velocity) of a
microscopic object like electron.
Macroscopic particle Heisenberg’s uncertainty principle
X
The uncertainties in the position and velocity of
objects with relatively large masses are negligible

Microscopic particle Heisenberg’s uncertainty principle

√
The uncertainties in the position and velocity of objects
with relatively microscopic masses have significant value W. Heisenberg

Heisenberg’s uncertainty principle holds significant value in the quantum world

If Δx is the uncertainty in defining Contradiction between Heisenberg’s uncertainty

the position and Δp is the uncertainty principle and Bohr concept:
in measuring momentum, then the
uncertainty principle may be Bohr’s Heisenberg’s
expressed mathematically as: atomic model uncertainty principle

Both the position Simultaneous determination

and velocity of an of exact position and the
electron can be exact velocity of electron
determined is impossible
Calculate the uncertainty in velocity of a cricket ball (mass=0.1kg) if the
uncertainty in position is of the order of 100pm.

According to Heisenberg’s uncertainty principle, 100 pm = 100X10-12m

= 10-10m

6.625X10-34
4X3.14X10-10X.1

5.28X10-24 m/s

Hence the uncertainty in velocity of this cricket ball is 5.28X10-24 m/s

The uncertainty in position and velocity of a particle are 10 -10 m and 5.27x
10-24 m/s respectively. Calculate the mass of particle.
According to Heisenberg’s uncertainty principle,

m h
4p. Dv . Dx

6.626X10-34
4x3.14x5.27X10-24x10-10

0.1 kg

Hence the mass of particle is 0.1 kg.

From Heisenberg’s uncertainty principle show that, electron
can’t exist in nucleus (radius of nucleus = 10-14 cm).

Radius of the nucleus is of the order of 10-14 cm and thus uncertainty in

position of electron, i.e. (Δx), if it is within the nucleus will be 10-14 cm.

Now,

Δv ≥ 6.626×10-27/(4×3.14×9.108×10-28×10-14)
Δv ≥ 5.79×1013 cm/sec.

Hence, the velocity of electron is 5.79×1013 cm/sec

i.e., order of velocity of electron will be 1000 times greater than the
velocity of light (3×1010cm/sec) which is impossible. Thus, possibility of
electron to exist in nucleus is zero.

Thus, possibility of electron to exist in nucleus is zero.

 Drawback of Bohr’s atomic model
1. It is valid for one electron atoms, eg. H, He+,Li2+,Be3+,etc.
2. Orbits were taken as circular but according to Sommerfield these
are elliptical.
3. Intensity of spectral line could not be explained.
4. It could not explained the minute structure in spectral line.
5. This does not explain the Zeeman’s effect (the splitting of spectral
lines in magnetic field) and Stark effect (the splitting of spectral lines
in electric field).
6. According to Heisenberg’s uncertainty principle, the position as well
velocity of a moving electron cannot be measure accurately at one time.
So the Bohr’s concept of stationary orbit where electron moves with
constant speed at a fixed radius around the nucleus is practically not
possible.
7. Additional difficulties appeared in connection to appearance of multiple
structure of certain elements which are quite widely separated relative to
fine structural lines explained by Sommerfield. The well known Na-line of
5895.93Ǻ and 5889.96 Ǻ are example of a doublet. This require the
introduction of a forth quantum number called spin quantum number‘s’.
The kinetic energy of a subatomic particle is 5.85x 10-25 J. Calculate the frequency
of particle wave (h=6.626×10−34Js).

We know, l= c/n .........(i)

Where l = wavelength
c = velocity of light
n = frequency
If particle moves with velocity of light then ‘c’ can be
replaced with ‘v’ in the above equation. Hence equation (i)
Becomes,
l= v/n .........(ii)

According to de Broglie hypothesis, l= h/p = h/(mv)

v/n = h/(mv) (from eq ii)
mv2 = nh .........(iii)

Kinetic energy = v2 = nh

n = (2 x K.E)/h
= (2 X 5.85 x 10-25)/6.626 x 10−34
= 1.76x109 s-1

Hence, the frequency of particle wave is 1.76x109 s-1

 Three dimensional
Quantum mechanical model of atom model of atom

considered fixed position of We may get only It is described

Electron as Wave electron can not probable location as probability of
be located of electron finding an
not
electron in a
considered
particular
as This 3D
when electron behave like location/region
particle then position and location is in space.
particle velocity of an electron must called Orbital
be known exactly as electrons
are present in Orbit

needs
To represent electron as Wave An Equation Schrodinger’s wave equation

Schrodinger’s wave equation provides a satisfactory description of an atom. The well

known form of Schrodinger’s wave equation is as follow:

E= Total energy, V= Potential energy of the

system, m= mass of electron, h= Planck’ constant
2 = Laplacian Operator
2 
 = Amplitude of the wave

After Solving Schrodinger’s wave equation

Several Solutions for  are obtained

 Many of these solutions are imaginary
and hence they are not valid

Solutions for  present in

Schrodinger’s wave equation

Only those values of  are valid which

satisfy the following conditions.

When  satisfies these • must be continuous

conditions is  called • must be finite
Eigen Function & its • must be single valued
valid solutions are called • must be normalized that means
Eigen Values. they must satisfy the relation

The probability of finding

the electron in orbital
Four Qunantum Numbers (+∞ to -∞) must be equal
to 1. This is the
n (Principal Quantum Number), means significance of  2
l (Azimuthal Quantum Number),
m (Magnetic Quantum Number) Three valid variables as solution are
and s (Spin Quantum Number) obtained by which 3D location of
electron can be represented

There is a 4th Qunantum Number (s) n,l and m These three variables are
which is not the solution of Qunantum three Qunantum Numbers
Schrodinger’s wave equation Numbers
 NOTE
Four Qunantum Numbers Shells (K,L,M,N, etc)
divided into
n, l and m s Sub-shells or orbit
(s, p, d, f)
Location of electron in Direction of rotation further divided into
orbital can be identified (clockwise and anticlockwise)
of an electron can be said Orbitals
Orbital is 3D residence of
electron where probability of
Principal Quantum Number (n) finding electron is maximum

 Principal quantum number (n) is used to designate the principal electron shell of the atom.
 The value of the principal quantum number can be any integer with a positive value that is
equal to or greater than one.
The value n=1 Kth shell (innermost shell or the ground state)
n=2 Lth shell Energy increases
n ≠ 0 n=3 Mth shell E=-13.6(Z2/n2) eV
n=4 Nth shell
 Principal quantum number (n) is used to describe the probable distance between the nucleus
and the electrons. Larger value of the “n” implies a greater distance between the electron and
the nucleus which, in turn, implies a greater atomic size)
n=1 Kth shell (innermost shell or the ground state) distance between the
electron and the nucleus
Value of ‘n’ n=2 Lth shell increases
increases n=3 Mth shell
Atomic Size increases
n=4 Nth shell

Principal Quantum Number (n) is used to comment on Orbital Size

Azimuthal Quantum Number (l)
 The azimuthal quantum number (l ) is also called orbital angular momentum.
 The value of ‘l ’ depends on the principal quantum number (n), i.e. the value of the
azimuthal quantum number ranges from 0 to (n-1).
 For different values of ‘l ’ different subshells are generated.
l =0 s-subshell spherical shape
l =1 p-subshell dumbbell shape
l =2 d-subshell double dumbbell shape
l =3 f-subshell complecated 8-fold shape

 The azimuthal (or orbital angular momentum) quantum number describes the shape
of a given orbital.

 Shell n l Subshell No. of

Subshell
How many number of subshell in a shell?
K 1 0 1s 1
L 2 0,1 2s, 2p 2 Ans: The number of subshell in a shell is
equal to the value of principal quantum
M 3 0,1,2 3s,3p,3d 3 number (n). For example, there are four
N 4 0,1,2,3 4s,4p,4d,4f 4 subshells in nth shell (n=4).

Azimuthal Quantum Number (l) is used to comment on Orbital Shape

Magnetic Quantum Number (m)
 The magnetic quantum number (m) says about the orientation of orbitals.
 The value of ‘m’ depends on the azimuthal quantum number (l), i.e. the value of the
magnetic quantum number ranges from + l to - l.
 The total number of orbitals in a subshell = (2 l +1)
 The total number of orbitals in a shell = n2
 Number of electron in an orbitals is = 2
m orbital No. of
orbital
0 s 1

-1,0,+1 px, py, pz 3

-2,-1,0,+1,+2 dxy, dyz, dz2, dxz, dx2-y2 5

-3,-2,-1,0,+1,+2,+3 fx(x2-3y2), fy(x2-z2), fxz2, fz3, fyz2, fxyz, fy(3x2-y2) 7

Spin Quantum Number (s)
 The spin quantum number is independent of the values of n, l, and m.
 The value of this number gives insight into the direction in which the electron is
spinning.
 The possible values of the electron spin quantum number are +½ and -½.
 The positive value of ‘s’ implies an upward spin on the electron which is also
called ‘spin up’ and is denoted by the symbol ↑. If ‘s’ has a negative value, the
electron in question is said to have a downward spin, or a ‘spin down’, which is
given by the symbol ↓.
 The value of the electron spin quantum number determines whether the atom in
question has the ability to produce a magnetic field. The value of ‘s’ can be
generalized to ±½. n
l

s
Write down the possible values of four quantum numbers for the valence electrons
of calcium (Ca-20). valence
electron
Ans: Electronic configuration of Ca: 1s²2s²2p⁶3s²3p⁶ 4s²
The valence orbital is 4s hence, n=4
As s-orbital is considered hence, l=0
The value of m should be –l to +l hence, m=0
As two two electrons are present in 4s hence, s=+1/2 and -1/2

What is the value of magnetic quantum number corresponds to px orbital?

Ans: As the given orbital is a p-orbital so its ‘l’ value should be 1. Now, the
possible ‘m’ values are -1 to +1 i.e. -1, 0, +1. Hence for px orbital the m=-1 (see
the chart in next page).

What are the Possible m values for l = 4?

Since the value of the magnetic quantum number ranges from -l to l, the possible
values of m when l = 4 are: -4, -3, -2, -1, 0, 1, 2, 3, and 4.

What is the symbol of orbital having n=4 and l=3?

Ans: The symbol is 4f. (l =3 means f-subshell; as principal quantum no. is 4, so
symbol is 4f )

Write the possible values of ‘m’ along with their symbols (designated orbital) for an
electron with l=2 value.
Ans: For l=2, the subshell should be ‘d’.
Possible ‘m’ values are -2 to +2 i.e. -2, -1, 0, 1, and 2.
Designated orbitals/symbols are--- 3dxy, 3dyz, 3dz2, 3dxz, 3dx2-y2
 Summary
Principle Azimuthal Magnetic Quantum Symbol No. of No. of
Quantum Quantum number orbitals in orbitals
number number (m) subshell in shell
(n) (l) (2l+1) (n2)

1 0 0 1s 1 1

2 0 0 2s 1
(1+3)=4
2 1 -1, 0, +1 2px, 2pz, 2py 3

3 0 0 3s 1

3 1 -1, 0, +1 3px, 3pz, 3py 3

(1+3+5)
3 2 -2, -1, 0, +1, +2 3dxy, 3dyz, 3dz2, 3dxz, 5 = 9
3dx2-y2
4 0 0 4s 1

4 1 -1, 0, +1 4px, 4pz, 4py 3

4 2 -2, -1, 0, +1, +2 4dxy, 4dyz, 4dz2, 4dxz, 5

4dx2-y2 (1+3+5+
7) = 16
4 3 -3, -2, -1, 0, +1, +2, 4fx(x2-3y2), 4fy(x2-z2), 7
+3 4fxz2, 4fz3, 4fyz2,
4fxyz, 4fy(3x2-y2)
Three quantum numbers n, l and m are needed to define an orbital.
Each orbital can hold up to two electrons, provided they have opposite
spins. Thus a fourth quantum number called spin quantum number s is
needed to define the spin of electron in an atom.

Pauli Exclusion Principle:

No two electrons in one atom can have their four quantum numbers the
same.

Hund’s rule:
Electrons will fill all the degenerate orbitals with parallel spins
first before pairing up in one orbital.

Aufbau’s Principle:
Aufbau (German aufbauen, “to build up”) principle tells us that electrons
fill the orbitals in the order of increasing their energy level.
 Nodal plane in an atomic orbital
Nodal plane is a plane that passes through a nucleus where the probability
of finding an electron is almost zero.
Draw the shape of dxy, dyz and dxz orbital
mentioning their nodal planes

Nodal planes for dxy are xz-plane and yz-plane

Nodal planes for dyz are xy-plane and xz-plane
Nodal planes for dxz are xy-plane and yz-plane
 Particle in one dimensional box
A particle in a 1-dimensional box is a fundamental quantum mechanical approximation
describing the translational motion of a single particle confined inside an infinitely
deep well from which it cannot escape. The solutions to the problem give possible
values of E and ψ that the particle can possess. E represents allowed energy values
and ψ(x) is a wave function, which when squared gives us the probability of locating
the particle at a certain position within the box at a given energy level.

Now if we consider a particle bouncing back and froth between two wall in an one
dimensional box. The box is infinitely long. Assume that the particle moves in this
box only along the vertical axis at x=0 and x=L. There is no forces acting on the
particle inside the box, so its potential energy is zero.
Here, V = 0 for 0<x<L
V = ∞ for x<0 or x>L
By putting the value of potential energy V = 0,
the Schrodinger equation becomes

8p2mE
+ ψ(x) = 0
h2
Any solution to this equation will take

ψ(x) = A sin( x) + B cos( x) where A and B are constants

 The solution to the Schrödinger equation we found here is the general solution for a
1-dimensional system. We now need to apply our boundary conditions to find the
solution to our particular system.
According to our boundary conditions, the probability of finding the particle at x=0
or x=L is zero. When x=0, sin(0) = 0 and cos(0) = 1 therefore, B must equal 0 to
fulfill this boundary condition giving:
ψ(x) = B sin( x)

Now applying x = L and ψ(L) = 0

or, 0 = B sin( L)

either B=0 or the sin term is 0.

Now B cannot be 0 because it is a constant term.

Hence, sin( L) = 0 = sin(np)

or, L = np

or, E = Where, n = 1, 2, 3…

This is an important result that tells us the energy of a particle is quantized and the
lowest possible energy of a particle is NOT zero. This is called the zero-point energy
and means the particle can never be at rest because it always has some kinetic
energy.
This is also consistent with the Heisenberg Uncertainty Principle: if the particle had
zero energy, we would know where it was in both space and time.

The wave function ψ and probability ψ2 of finding for a particle in a box at the
n=1and n=2 energy levels look like this:

Notice that the number of nodes (places where the particle has zero probability of
being located) increases with increasing energy n. Also note that as the energy of
the particle becomes greater, the quantum mechanical model break down as the
energy levels get closer together and overlap, forming a continuum. This continuum
means the particle is free and can have any energy value. At such high energies,
the classical mechanical model is applied as the particle behaves more like a
continuous wave. Therefore, the particle in a box problem is an example of Wave-
Particle Duality.
Write the wave function and the total energy of particle in a one-dimensional
box for n=2 state. Indicate the number of nodes in the wave.

The wave function of particle in a one-dimensional box for nth state is

Any solution to this equation will take

ψ(x) = A sin( x) + B cos( x)

The total energy of particle in a one-dimensional box for nth state is

4h2 h2
For n = 2 state, E2
2mL2

For n = 2 state, the number of

nodes in the wave is one.

One node
 Possible Questions
1. Calculate the wavelength of emitted light for the electronic transition from
n=4 to n=1 energy level for the hydrogen atom. In which region of
electromagnetic spectrum does this radiation fall? (RH=1.096776x107m-1).

2. In which region of the electromagnetic spectrum of hydrogen atom does the

Lyman series exist? Write the limitations of Bohr’s theory.

3. State and explain de Broglie’s principle for the wave particle duality.

4. What is the importance of de Broglie’s relation? Consider a beam of electron

with a speed of 5.31x106 m/s, calculate the de Broglie wavelength (Mass of
electron = 9.11x10-31 kg; h=6.626×10−34Js).

5. Kinetic energy of a subatomic particle is 5.85x10-25 J. Calculate the

frequency of the particle wave. (Given Plank’s constant, h= 6.6x10 -34kg m2s-1)

6. What does the term stationary state of an electron signifies? Can we apply
Heisenberg uncertainty principle to a stationary electron?

7. The uncertainty in the position and velocity of a particle are 10 -10 m and
5.27x10-24 ms-1 respectively. Calculate the mass of the particle.
(h=6.626×10−34Js)

8. Write down the Schrodinger’s wave equation mentioning the terms involved in
the equation.
9. What is ? What information is conveyed by  and  2?

[Link] are the names, symbols and significances of the four quantum numbers?

[Link] down the possible values of four quantum numbers for the valence
electrons of calcium (Ca-20).

12. Write the possible values of m for an electron with l=3 and with l=2.

13. Draw the shapes of px, py and pz orbital along the x, y, z axes with proper
labeling.

14. What do you know about the nodal plane in an atomic orbital? Draw the shape
of dxy, dyz and dxz orbital mentioning their nodal planes.

15. State and explain Pauli’s exclusion principle.

16. Write the wave function and the total energy of particle in a one-dimensional
box for n=2 state. Indicate the number of nodes in the wave.