MSP-607 Atomic and Molecular Physics

Dr. Ajeetkumar Patil

ajeetkumar.p@manipal.edu
 MSP 607: Atomic and Molecular Physics
❖ Unit – I: Atomic Spectra: Electromagnetic spectrum, types of molecular
energies, different spectroscopic methods, spectral line width, absorption and
emission of radiation, Einstein’s coefficients, quantum states of electron in
atoms, hydrogen atom spectrum, electron spin, Stern Gerlach experiment, spin-
orbit interaction, Lande interval rule, two electron systems, LS-JJ coupling
schemes, fine structure, spectroscopic terms and selection rules, hyperfine
structure, exchange symmetry of wave function, Pauli's exclusion principle,
periodic table, alkali type spectra, equivalent electrons, Normal and anomalous
Zeeman effect, Paschen Back Effect, Stark effect, lamb shift. 10 hours
❖ Unit–V:Spectroscopic techniques and instrumentation: Spectrographs,
monochromators and interferometers (Michelson, Mach-Zander and Fabry-
Perot), UV- Visible, Infra-red, Raman and Laser Induced Fluorescence
spectroscopic techniques and its instrumentation. Introduction to NMR, NMR
Instrumentation, Introduction to ESR, Introduction to Mössbauer spectroscopy.
Applications of Mossbauer spectroscopy. 10 hours
❖ Unit-VI: Atomic Collisions: Basic concepts and potential scattering, types of
collisions, thresholds and cross-sections, Electron –atom collisions and atomic
photoionisation, atom-atom collisions, elastic &inelastic collisions. 5 hours
 Atomic & Molecular Physics
Spectroscopic
Experiments
Electronic Structural information
Electronic energy levels
Stationary states information In terms of
Time dependence basic concept
such as
electrons,
photons &
Quantum quantum states
Mechanics
Theory
Subject development for Predictive capability
understanding observables
➢The science includes light emission, transmission,
deflection, amplification and detection by optical
components and instruments, lasers and other light
sources, fiber optics, electro-optical instrumentation,
related hardware and electronics, and sophisticated
systems.
➢ The range of applications of photonics extends from
energy generation to detection to communications
and information processing.
 History of the subject
◼ In 1666, NEWTON
band of colors of sunlight by prism

◼ In 1817, Fraunhofer
several hundreds lines of solar system

◼ In 1860, Foucault
Powerful arc source through Na- vapors ,
two D-lines match with the sun’s spectrum S
C
R
Arc Source Na Vapors E
E
In 1860, Kirchoff – Sun is surrounded by layers N
of
gases acting as absorption screen
◼ In 1868, Angstrom → published the elaborate
map of solar spectrum, accurate measurement
of the solar lines.
◼ Angstrom introduced UNIT for the wavelength 1Å = 10 nm =10-8 cm

◼ In 1882, Rowland → developed

ruling grating & published a photographic map
of the solar system
◼ In 1882, → Balmer published Hydrogen lines
“BALMER SERIES”
within experimental limit, the empirical
formula
In 1900,Planck proposed E = h (radiation quantization)
Einstein proposed h = Ws +½mv2(photoelectric effect)

In 1911,
Rutherford did the -scattering experiment & gave the model of atom
“the negative charge (electrons) are rotating in a obit like planetary
motions around the heavy positive charge (nucleus)”
BOHR retained the Rutherford model but introduced the quantization
of atom by assuming “An electron could only occupy certain specific
circular orbits allowed by a quantum condition, namely, that the angular
momentum of the electron about the nucleus should be an integral
multiple of h/2 “
In 1913, Franck & Hertz independently proved the quantum
nature of atomic energy levels

G
I

V 2V 3V

➢First experiment to probe the energy levels of an atom and

supported Bohr atom model
➢The existence of excited states
➢Confirmed the quantum theory
➢electrons occupies only discrete, quantized energy states
 Shortcomings of Bohr Theory

◼ Unsuccessful in explaining many experimental

observations such as intensities both in emission &
absorption
◼ Could not account for complex atoms than hydrogen
◼ Could not explain why non-integral quantum
numbers are required in empirical formula for
complex atoms
In 1924, L. de Broglie → first suggested that the possibility of
treating electrons mathematically as if the waves rather than particles,
so that quantum conditions emerge naturally as part of the analysis

h
=
p

Classical analog to vibrations & oscillation of a mechanical string

Standing wave condition

2a = n
In 1926, Schrodinger
There is no reason to retain even Bohr’s electron orbits.

Total energy E = T + V
Schrodinger’s Equation :
Atomic Model
 Bohr Model
• In 1913, the Danish
scientist Niels Bohr
proposed a model. He
placed each electron
in a specific energy
level.
Bohr Model
• According to Bohr’s
atomic model,
electrons move in
definite orbits
around the nucleus,
much like planets
circle the sun.
• These orbits, or
energy levels, are
located at certain
distances from the
nucleus.
 Bohr’s Model

Nucleus

Electron

Orbit

Energy Levels
The Wave Model

• Today’s atomic model is

based on the principles
of wave mechanics.
• According to the theory
of wave mechanics,
electrons do not move
about an atom in a
definite path, like the
planets around the sun.
Wave Model
 The Wave Model
• In fact, it is impossible to determine the exact
location of an electron. The probable location of an
electron is based on how much energy the electron
has.
• According to the modern atomic model, at atom has
a small positively charged nucleus surrounded by a
large region in which there are enough electrons to
make an atom neutral.
 Electron Cloud:
• A space in which
electrons are likely to
be found.
• Electrons whirl about
the nucleus billions of
times in one second
• They are not moving
around in random
patterns.
• Location of electrons
depends upon how
much energy the
electron has.
 Electron Cloud:

• Depending on their energy they are locked into a

certain area in the cloud.
• Electrons with the lowest energy are found in the
energy level closest to the nucleus
• Electrons with the highest energy are found in the
outermost energy levels, farther from the nucleus.
 The Electron Cloud
The higher the
electron density,
the higher the
probability that
an electron may
be found in that
region.

http://www.chemeng.uiuc.edu/~alkgrp/mo/gk12/quantum/H_S_orbital.jpg
The Electron Cloud for Hydrogen

90% probability
of finding the
electron within
this space
Development of Atomic Models
Thomson model
In the nineteenth century, Thomson described
the atom as a ball of positive charge containing
a number of electrons.
Bohr model
After Rutherford's discovery, Bohr proposed
that electrons travel in definite orbits around
the nucleus.
Rutherford model
In the early twentieth century, Rutherford
showed that most of an atom's mass is
concentrated in a small, positively charged
region called the nucleus.
Quantum mechanical model
Modern atomic theory described the
electronic structure of the atom as the
probability of finding electrons within
certain regions of space.
 Indivisible Electron Nucleus Orbit Electron
Cloud
Greek √
Dalton √
Thomson √
Rutherford √ √
Bohr √ √ √
Wave √ √ √
 Electromagnetic spectrum
• The electromagnetic spectrum is the distribution of
electromagnetic radiation according to energy.
• The electromagnetic spectrum covers a wide range
of wavelengths and photon energies. Light used to
"see" an object must have a wavelength about the
same size as or smaller than the object.
• It is the range of all possible frequencies of
electromagnetic radiation.
Regions of the Electromagnetic Spectrum
Spectrum of Electromagnetic Radiation
Region Wavelength Wavelength Frequency Energy
(Angstroms) (centimeters) (Hz) (eV)
Radio > 109 > 10 < 3 x 109 < 10-5

Microwave 109 - 106 10 - 0.01 3 x 109 - 3 x 1012 10-5 - 0.01

3 x 1012 - 4.3 x
Infrared 106 - 7000 0.01 - 7 x 10-5 0.01 - 2
1014
7 x 10-5 - 4 x 10- 4.3 x 1014 - 7.5 x
Visible 7000 - 4000 5 2-3
1014
7.5 x 1014 - 3 x
Ultraviolet 4000 - 10 4x 10-5 - 10-7 3 - 103
1017
3 x 1017 - 3 x
X-Rays 10 - 0.1 10-7 - 10-9 103 - 105
1019
Gamma Rays < 0.1 < 10-9 > 3 x 1019 > 105
 = c/
Atomic Absorption and Emission spectra
Light: Particle or a Wave…….?????
 Quantum Numbers
Electrons can be labelled using the subshell
and orbital or by using the four quantum
numbers:
➢ n : principal quantum number
➢ l : azimuthal quantum number
➢ ml : magnetic quantum number
➢ ms : spin quantum number
Principal Quantum Number, n
➢The principal quantum number, n, is always a
positive integer and tells us the energy level or
shell that the electron is found in.
➢The maximum number of subshells permitted for
a particular shell is equal to n2.
➢The maximum number of electrons permitted in a
particular shell is equal to 2 x n2.
n Energy Level Shell No. Subshells = n2 No. electrons = 2n2
1 1st energy level K 1 2
2 2nd energy level L 4 8
3 3rd energy level M 9 18
4 4th energy level N 16 32
Azimuthal Quantum Number, l
➢The azimuthal quantum number tells us which
subshell the electron is found in, and therefore it
tells us the shape of the orbital.
➢l can have values ranging from 0 to n-1.
➢The number of orbitals permitted for a particular
subshell is equal to 2l + 1.

Value of n l=n-1 Subshell (orbital shape) No. orbitals = 2l + 1 Value of n

1 0 s subshell 1 (1 x s orbitals) 1
2 1 p subshell 3 (3 x p orbitals) 2
3 2 d subshell 5 (5 x d orbitals) 3
4 3 f subshell 7 (7 x f orbitals) 4
Magnetic Quantum Number, ml
➢The magnetic quantum number, ml, tells us the
orientation of an orbital in space.
➢ml can have values ranging from -l to +l.
➢It is not always possible to associate a value of ml with
a particular orbital.
Value of l Subshell Values of ml Possible orbitals
0 s 0 s
1 p -1, 0, 1 px, py, pz
2 d -2, -1, 0, 1, 2 dxy, dxz, dyz, dx2-y2, dz2
3 f -3, -2, -1, 0, 1, 2, 3

Spin Quantum Number, ms

➢The spin quantum number, ms, tells us the spin of the
electron.
➢ms can have a value of +½ or -½.
Shape of s orbitals
 Number of Orbital Number of
n l ml (-l to +l)
orbitals name electrons

1 0 0 1 1s 2

2 0 0 1 2s 2

1 -1, 0, +1 3 2p 6

3 0 0 1 3s 2

1 -1, 0, +1 3 3p 6

2 -2, -1, 0, +1, +2 5 3d 10

4 0 0 1 4s 2

1 -1, 0, +1 3 4p 6

2 -2, -1, 0, +1, +2 5 4d 10

3 -3, -2, -1, 0, +1, +2, +3 7 4f 14

 Aufbau Principle
• The aufbau principle says that the arrangement of electrons in
an atom - the electron configuration - is best understood if it is
built from the ground up.
• 'Aufbauprinzip' is a German noun; it means 'construction
principle. Aufbau rules are:
1. Electrons are placed in the lowest energetically available subshell.
2. An orbital can hold at most 2 electrons.
3. If two or more energetically equivalent orbitals are available (e.g., p, d
etc.) then electrons should be spread out before they are paired up
(Hund's rule).

Pauli's Exclusion Principle

• The Pauli exclusion principle says that every electron must be
in its own unique state.
• In other words, no electrons in an atom are permitted to have
an identical set of quantum numbers.
 Hund's Rule
• The Aufbau principle says how that electrons fill the lowest
energy orbitals first, and then move up to higher energy orbitals
only after the lower energy orbitals are full.
• There a problem with this rule: Certainly, 1s orbitals should be
filled before 2s orbitals, because the 1s orbitals have a lower
value of n, and thus a lower energy. What about the three
different 2p orbitals? In what order should they be filled?
• The answer to this question involves Hund's rule. Hund's rule
states that:
1. Every orbital in a sublevel is singly occupied before any
orbital is doubly occupied.
2. All of the electrons in singly occupied orbitals have the same
spin (to maximize total spin).
• When assigning electrons to orbitals, an electron first seeks
to fill all the orbitals with similar energy before pairing with
another electron in a half-filled orbital.
 Extended form of Periodic Table

https://courses.lumenlearning.com/introchem/chapter/the-bottom-of-the-periodic-table
Absorption and Emission
 Enf

∆E= (Enf - Eni)

Eni
e
http://webbook.nist.gov/chemistry/polyatom/
 Origin of Continuum, Emission,
and Absorption Spectra
▪ A continuum spectrum results when the gas pressures are
higher. Generally, solids, liquids, or dense gases emit light at
all wavelengths when heated.
▪ Emission spectra are produced by thin gases in which the
atoms do not experience many collisions (because of the low
density). The emission lines correspond to photons of
discrete energies that are emitted when excited atomic states
in the gas make transitions back to lower-lying levels.
▪ An absorption spectrum occurs when light passes through a
cold, dilute gas and atoms in the gas absorb at characteristic
frequencies; since the re-emitted light is unlikely to be
emitted in the same direction as the absorbed photon, this
gives rise to dark lines (absence of light) in the spectrum.
Types of Molecular spectra
• To obtain a molecular spectrum, the substance under
examination is exposed to electromagnetic radiations of a
series of wavelengths.
• Molecules of the substance absorb certain wavelengths in
order to be excited to higher electronic, vibrational or
rotational energy levels.
• The series of wavelengths absorbed in each case gives a
distinct molecular spectrum. Thus there are three main types
of molecular spectra.
Thus there are three main types of molecular spectra.
1. Electronic Spectra:
These are caused by absorption of high energy photons which can send electrons to
higher energy levels. The electronic spectra are within the visible or ultraviolet regions
of the electromagnetic spectrum.
2. Vibrational Spectra:
Lower energy photons cause changes in vibrational energy levels. The spectra thus
obtained are referred to as vibrational spectra. These are in the near infrared region
(near to the visible region).
3. Rotational Spectra:
Still lower energy photons cause changes in the rotational levels in the molecules.
These spectra are called the rotational spectra. These spectra are in the far infrared or
microwave region. In order to use numbers of reasonable size, different units are used
for different types of spectra. In ultraviolet and visible spectra the radiation is stated
as a wavelength in nm or as a wave-number in cm–1. In infrared spectra, wave-
numbers in cm–1 are often used. In microwave or NMR spectra, frequencies are
expressed in Hz (or MHz).
When energy of the incident photon is large enough to produce changes in electronic
levels, it can also bring, about changes in vibrational and rotational levels. Therefore
some spectra are electronic-vibrational-rotational spectra. Similarly, the photon that is
capable of bringing about changes in vibrational levels can also cause rotational energy
changes. Thus vibrational-rotational spectra result. Pure rotational spectra involve only
small energy changes which cannot bring about vibrational or electronic changes.
Franck–Condon principle
• Explains the intensity of vibronic transitions.
• Vibronic transitions are the simultaneous changes in electronic and
vibrational energy levels of a molecule due to the absorption or emission
of a photon of the appropriate energy.
• The principle states that during an electronic transition, a change from
one vibrational energy level to another will be more likely to happen if the
two vibrational wave functions overlap more significantly.
• Electronic transitions are essentially instantaneous compared with the
time scale of nuclear motions, therefore if the molecule is to move to a
new vibrational level during the electronic transition, this new vibrational
level must be instantaneously compatible with the nuclear positions and
momenta of the vibrational level of the molecule in the originating
electronic state.
• In the semiclassical picture of vibrations (oscillations) of a simple harmonic
oscillator, the necessary conditions can occur at the turning points, where
the momentum is zero.
The Franck-Condon Principle describes the intensities of vibronic transitions, or the
absorption or emission of a photon. It states that when a molecule is undergoing an
electronic transition, such as ionization, the nuclear configuration of the molecule
experiences no significant change. This is due in fact that nuclei are much more
massive than electrons and the electronic transition takes place faster than the
nuclei can respond. When the nucleus realigns itself with with the new electronic
configuration, the theory states that it must undergo a vibration.
Spectroscopy
• Spectroscopy is a technique that uses the interaction of energy with
a sample to perform an analysis.
• The data that is obtained from spectroscopy is called a spectrum. A
spectrum is a plot of the intensity of energy detected versus the
wavelength (or mass or momentum or frequency, etc.) of the
energy.
• A spectrum can be used to obtain information about atomic and
molecular energy levels, molecular geometries, chemical bonds,
interactions of molecules, and related processes. Often, spectra are
used to identify the components of a sample (qualitative analysis).
Spectra may also be used to measure the amount of material in a
sample (quantitative analysis).
• There are several instruments that are used to perform a
spectroscopic analysis. In simplest terms, spectroscopy requires an
energy source (commonly a laser, but this could be an ion source or
radiation source) and a device for measuring the change in the
energy source after it has interacted with the sample (often a
spectrophotometer or interferometer).
 Different spectroscopic methods
There are as many different types of spectroscopy as
there are energy sources! Here are some examples
• Astronomical Spectroscopy
Energy from celestial objects is used to analyze their chemical composition, density,
pressure, temperature, magnetic fields, velocity, and other characteristics. There are
many energy types (spectroscopies) that may be used in astronomical spectroscopy.
• Atomic Absorption Spectroscopy
Energy absorbed by the sample is used to assess its characteristics. Sometimes
absorbed energy causes light to be released from the sample, which may be
measured by a technique such as fluorescence spectroscopy.
• Attenuated Total Reflectance Spectroscopy
This is the study of substances in thin films or on surfaces. The sample is penetrated
by an energy beam one or more times and the reflected energy is analyzed.
Attenuated total reflectance spectroscopy and the related technique called frustrated
multiple internal reflection spectroscopy are used to analyze coatings and opaque
liquids.
• Electron Paramagnetic Spectroscopy
This is a microwave technique based on splitting electronic energy fields in a
magnetic field. It is used to determine structures of samples containing unpaired
electrons.
• Electron Spectroscopy
There are several types of electron spectroscopy, all associated with measuring
changes in electronic energy levels.
• Fourier Transform Spectroscopy
This is a family of spectroscopic techniques in which the sample is irradiated by all
relevant wavelengths simultaneously for a short period of time. The absorption
spectrum is obtained by applying a mathematical analysis to the resulting energy
pattern.
• Gamma-ray Spectroscopy
Gamma radiation is the energy source in this type of spectroscopy, which includes
activation analysis and Mossbauer spectroscopy.
• Infrared Spectroscopy
The infrared absorption spectrum of a substance is sometimes called its molecular
fingerprint. Although frequently used to identify materials, infrared spectroscopy
also may be used to quantify the number of absorbing molecules.
• Laser Spectroscopy
Absorption spectroscopy, fluorescence spectroscopy, Raman spectroscopy, and
surface-enhanced Raman spectroscopy commonly use laser light as an energy
source. Laser spectroscopies provide information about the interaction of
coherent light with matter. Laser spectrocopy generally has high resolution and
sensitivity.
• Mass Spectrometry
A mass spectrometer source produces ions. Information about a sample may be
obtained by analyzing the dispersion of ions when they interact with the sample,
generally using the mass-to-charge ratio.
• Multiplex or Frequency-Modulated Spectroscopy
In this type of spectroscopy, each optical wavelength that is recorded is encoded
with an audio frequency containing the original wavelength information. A
wavelength analyzer can then reconstruct the original spectrum.
• Raman Spectroscopy
Raman scattering of light by molecules may be used to provide information on a
sample's chemical composition and molecular structure.
• X-ray Spectroscopy
This technique involves excitation of inner electrons of atoms, which may be seen
as x-ray absorption. An x-ray fluorescence emission spectrum may be produced
when an electron falls from a higher energy state into the vacancy created by the
absorbed energy.
Jablonski diagram
• Illustrates the electronic states of a molecule and the
transitions between them.
• The states are arranged vertically by energy and grouped
horizontally by spin multiplicity.
• Nonradiative transitions are indicated by squiggly arrows and
radiative transitions by straight arrows.
• The vibrational ground states of each electronic state are
indicated with thick lines, the higher vibrational states with
thinner lines.
• The diagram is named after the Polish physicist Aleksander
Jabłoński.
 PROBLEM
• Calculate the wavelength of yellow light
emitted from a sodium lamp if the frequency
is
5.10 x 1014 Hz (5.10 x 1014 s-1)
List the known
c = 3.00 x 1010 cm/s wavelength (λ) = ? cm
Frequency (v) = 5.10 x 1014 s-1
C = λv λ=c
v

λ = 3.00 x 1010 cm/s = 5.88 x 10-5 cm

5.10 x 1014 s-1
Coupling Schemes of two electron systems
All the best ☺ ☺ ☺