Thermal de Broglie Wavelength

𝑉 ℎ
𝑞= Λ=
Λ3 2𝜋𝑚𝑘𝑇 1 2

 The quantity Λ has the dimensions of length and is called the thermal
wavelength or thermal de Broglie wavelength of the molecule.

 𝑞 is the total number of thermally accessible states, the average

𝑞
number of states per molecule is .
𝑁

𝑉 𝑉
 For this quantity to be large, 𝑞 >> 1, we require 3 >> 1. But is volume
𝑁Λ 𝑁
on single particle, which is related to average separation of particles
𝑉 1 3
by d = .
𝑁

 Therefore the condition for there being many states available per
𝑑3
molecule is therefore >> 1, and therefore 𝒅 >> 𝜦
Λ3

1
 Importance of Molecular Partition Function
 It contains all the information needed to calculate the thermodynamic
properties of a system of independent particles.

 𝑞 plays a role in statistical thermodynamics very similar to that played

by the wavefunction in quantum mechanics: 𝑞 is a kind of thermal
wavefunction.

 The total energy of the system relative to the energy of the lowest
state is 𝐸 𝑇 = 𝑁𝑖 ε𝑖 𝑁𝑖 𝑒 −𝛽ε𝑖
= −𝛽ε𝑖
𝑖 𝑁 𝒊𝑒

 The energy depends on the temperature because the populations of

the states depend on the temperature. Also the most probable
configuration is so strongly dominating,
𝑁 𝑑 −𝛽ε
𝐸 𝑇 = ε𝑖 𝑒 −𝛽ε𝑖 ε𝑖 𝑒 −𝛽ε𝑖 =− 𝑒 𝑖
𝑞 𝑑𝛽
𝑖
𝑁 𝑑 −𝛽ε 𝑁 𝑑 𝑁 𝑑𝑞
𝐸 𝑇 =− 𝑒 𝑖 =− 𝑒 −𝛽ε𝑖 =−
𝑞 𝑑𝛽 𝑞 𝑑𝛽 𝑞 𝑑𝛽
𝑖 𝑖
2
 Internal Energy and Molecular Partition Function
 ε0 = 0 (remember that we measure all energies from the lowest
available level), E(T) should be interpreted as the value of the internal
energy relative to its value at T = 0, U(0). Therefore, to obtain the
conventional internal energy U, we must add the internal energy at T =
0. 𝑈 𝑇 =𝑈 0 +𝐸 𝑇
𝑁 𝑑𝑞
𝐸 𝑇 =−
𝑞 𝑑𝛽
 The partition function may depend on variables other than the
temperature i.e q (N,V, T) (for example, the volume, number of
particles), the derivative with respect to β in above equation is actually
a partial derivative with these other variables held constant.
𝑁 𝜕𝑞
𝑈 𝑇 =𝑈 0 +−
𝑞 𝜕𝛽 𝑉

𝜕 ln 𝑞
𝑈 𝑇 = 𝑈 0 + −𝑁
𝜕𝛽 𝑉
 These two above equations confirm that we need to know only the
partition function (as a function of temperature) to calculate the
internal energy relative to its value at T = 0.
3
Recap: Combination of the 1st and 2nd Laws of
Thermodynamics

𝑑𝑈 = 𝑑𝑞 + 𝑑𝑤

𝑑𝑤𝑟𝑒𝑣 = −pdV

𝑑𝑞𝑟𝑒𝑣 = −TdS

∆𝑈 = 𝑞𝑣

Is energy dispersed or localized during

the above spontaneous change?

4
 The entry point into the molecular interpretation of the Second Law of
thermodynamics is Boltzmann’s insight that an atom or molecule can possess only
certain values of the energy, called its ‘energy levels’.

 The continuous thermal agitation that molecules experience in a sample at T > 0

ensures that they are distributed over the available energy levels.

 System of N particles with energy state {ε0, ε1, ε2…..), where ε0 is reference
energy, and equal to zero.

 Then distribution in each energy states can represented by {N0, N1, N2…..)

 Then total number of ways “W” energy can be distributed in N particles given by

𝑁! 𝑁𝑖 𝑒 −𝛽ε𝑖 𝑁𝑖
𝑊= 𝑁
= −𝛽ε𝑖 = 𝑒 − (ε𝑖−ε𝑗)𝛽
𝑁0 ! 𝑁1 ! 𝑁2 ! … 𝒊𝑒 𝑁𝑗

 Should the distribution of molecules over energy levels and the entropy be
connected?

5
 𝑺 = 𝒌 ln 𝑾

 W is the number of microstates, the ways in which the molecules of a system can
be arranged while keeping the total energy constant.

 When we measure the properties of a system, we are measuring an average

taken over the many microstates the system can occupy under the conditions
of the experiment.

 The concept of the number of microstates makes quantitative the ill-defined

qualitative concepts of ‘disorder’ and ‘the dispersal of matter and energy’ that
are used widely to introduce the concept of entropy.

 The statistical entropy behaves in exactly the same way as the thermodynamic
entropy because as the temperature is lowered, the value of W, and hence of S,
decreases because fewer configurations are consistent with the total energy.

 In the limit T → 0, W = 1, so ln W = 0, because only one configuration (every

molecule in the lowest level) is compatible with E = 0. It follows that S → 0 as T
→ 0, which is compatible with the Third Law of thermodynamics, that the
entropies of all perfect crystals approach the same value as T → 0.

6
 Is any relationship between Partition Function (q)
and Entropy?

 𝑞 plays a role in statistical thermodynamics very similar to that played

by the wavefunction in quantum mechanics: 𝒒 is a kind of thermal
wavefunction. It contains all the information needed to calculate the
thermodynamic properties of a system of independent particles.

𝑵 𝒅𝒒
𝑺 𝑻 =− + 𝑵𝒌 𝒍𝒏 𝒒
𝑻𝒒 𝒅𝜷

7
 Linking microscopic and bulk thermodynamic properties.
 classical thermodynamics, & compare statistical properties of microstates.

Classical Thermodynamics Statistical Thermodynamics

 Empirical Evidence  Based on QM/CM, and distribution
of properties for large particles
 Macroscopic (Average Time & Space ) based on probabilistic laws.

 Equilibrium (well defined Properties)  Microscopic (Average N particles)

 Equation of state (Empirical) PV=nRT  Quantify the properties (well

for Ideal gas. defined)

 Laws of Thermodynamics  Connects molecular structure to

measurable Thermodynamic
properties

 Through systems determine the microscopic picture, and compare with

macroscopic thermodynamic properties.
8
 What you need to know from this lecture?

 Explain what is meant by an ensemble and why it is useful in statistical

thermodynamics.

 Under what circumstances may identical particles be regarded as

distinguishable?

 Identify the systems for which it is essential to include a factor of

1/N! on going from Q to q:
(a) a sample of helium gas
(b) a sample of carbon monoxide gas
(c) a solid sample of carbon monoxide
(d) water vapour.
(e) a sample of carbon dioxide gas
(f) a sample of graphite
(g) a sample of diamond
(h) ice.

9
 How to extend statistical thermodynamics for
interacting molecules?
 The crucial new concept we need when treating systems of interacting
particles is the ‘ensemble’, which means collection coined by J. Willard
Gibbs (1901), which turns to be crucial for dealing statistical sample.

 Ensemble average enables to determine time-average

thermodynamic properties.

 To set up an ensemble, we take a closed system of

specified volume, composition, and temperature, and
think of it as replicated 𝑵 times.
 Thermal contact with each other so they can exchange
energy. Total Energy is 𝑬
 This imaginary collection of replications of the actual
system with a common temperature is called the
canonical ensemble.
 The word ‘canon’ means ‘according to a rule’.

10
 What are the types of Ensemble possible?

 Canonical ensemble: N, V, T common: The imaginary collection of

replications of the actual system with a common temperature, volume,
and number of particles is called the canonical ensemble. The each
system is individually a closed system.

 Microcanonical ensemble: N, V, E common: The imaginary collection

of replications of the actual system with a common energy, volume, and
number of particles is called the microcanonical ensemble. The each
system is individually a isolated system.

 Grand canonical ensemble: μ, V, T common: The imaginary collection

of replications of the actual system with a common temperature,
volume, and chemical potential is called the grand canonical ensemble.
The each system is individually a open system, which means that
matter can be imagined as able to pass between the systems; the
composition of each one may fluctuate, but now the chemical potential
is the same in each system.

11
 Time-averaged thermodynamic properties.

 What one mean by time average?

 Imagine you want to detect a optical photon (1014 Hz) using a modern
detector, whose integration time larger than 10-10 sec. Can you
determine the time fluctuation of optical photon (electromagnetic
wave)?

 No, you can only measure time-average.

 Human Eye: Image is retained for only 1/16 second.

 Now consider a measurement of thermodynamic properties like

pressure, temperature and Volume of a system. The system consists of
matter, which are constantly moving in the order of time scale much
smaller than the measuring time. Then the measured quantities are
time averaged. Similarly measured thermodynamic properties are
spatially averaged.

12
 Microstate and Macrostate

 The total number of particles at energy level j is called the occupation

number Nj at that level, which decides the macrostate of the
assembly.

 Microstates are the possible ways in which the particles of an

assembly might be distributed among the energy states.
Four Distinguishable Molecules in two bulbs.

Macrostate: {4,0} {3,1} {2,2} {1,3} {0,4}

Number of Microstate:
13
1 4 6 4 1
 Introduction to Ensemble Average
 The total energy and number of particles must be constant for a
isolated/closed system. This restricts the possible microstates i.e the
possible ways in which the particles of an assembly might be
distributed among the energy states.

 How changes happen in the number of particles occupying the energy

states?

 Interactions: collision between the molecules, molecules colliding wall

of the container, and oscillating molecules in the crystal.

 The fundamental postulate of statistical thermodynamics is that all

possible or accessible microstates of an isolated assembly in
equilibrium are equally probable.

 It implies for a system at equilibrium, the thermodynamic state

(macrostate) which could result from the largest number of
microstates is also the most probable macrostate of the system.
14
 Microcanonical Ensemble
Microcanonical ensemble: N, V, E common: The imaginary collection of
replications of the actual system with a common energy, volume, and
number of particles is called the microcanonical ensemble. The each
system is individually a isolated system.
 Consider millions of ideal thermoflask containing hot water
of fixed number of water molecules, volume and energy
(N,V,E).
 Each thermoflask is macrostate because (N,V,E) constant.
But position and orientations of water molecules
are not controlled in each of the thermoflask, which
implies different and huge number of microstates.
 But each of the microstates are equal probable
because each thermoflask the total energy is
constant.

The fundamental postulate of statistical thermodynamics is that all

possible or accessible microstates of an isolated assembly in equilibrium
15
are equally probable.
 At any instant among billions of replicas, we found millions of
replicas (∆𝑵) are there in this microstate.

 Then, we can infer at any instant there will be millions of replicas

for all possible microstates because of equal probability of
microstate.

 We found that one of the macrostate (thermoflask 1) resides in

this microstate for milli sec (∆𝒕).

 Then, we can infer that all possible microstates will reside for
milli sec because of equal probability of microstate. 16
 Configuration of Ensemble

 The important point about an ensemble is that it is a collection of

imaginary replications of the system, so we are free to let the
number of members be as large as we like; when appropriate, we can let
𝑵 become infinite.

 Note that Ñ is unrelated to N, the number of molecules in the actual

system; Ñ is the number of imaginary replications of that system.

 The number of members of the ensemble in a state with energy Ei is

denoted Ñi

 Then total number of ways “𝑾” energy can be distributed in 𝑵

members of the ensemble
𝑵!
𝑾=
𝑵0 ! 𝑵1 ! 𝑵2 ! …
17
 Dominant Configuration
Four Distinguishable Molecules in two bulbs.

4! 4! 4! 4! 4!
𝑊= = = = =
4! 0! 3! 1! 2! 2! 1! 3! 0! 4!
1000 Distinguishable Molecules in two bulbs.
1000!
𝑊𝑀𝑃𝐷 = = 10301 𝑊𝑀𝑃𝐷 ≠ 𝑊 𝑇𝑜𝑡𝑎𝑙 𝑊𝑇𝑜𝑡𝑎𝑙 = 21000
500! 500!
693.08 = ln 𝑊𝑀𝑃𝐷 = ln 𝑊𝑇𝑜𝑡𝑎𝑙 = 693.15 18
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map:_Chemistry_-_The_Central_Science_(Brown_et_al.)/19:_Chemical_Thermodynamics/19.02:_Entropy_and_the_Second_Law_of_Thermodynamics
 Canonical Partition Function

 The configuration of greatest weight, subject to the constraints that

the total energy of the ensemble is constant at 𝑬 and that the total
number of members is fixed at Ñ, is given by the canonical
distribution:
𝑵𝒊 𝒆−𝜷𝑬𝒊 𝒆−𝜷𝑬𝒊
= −𝜷𝑬
=
𝑵 𝒊𝒆
𝒊 𝑸
 The quantity Q , which is a function of the temperature, is called the
canonical partition function.

 Canonical distribution gives the probability of occurrence of members

in a single state i of the entire system of energy Ei.

𝑬𝒊 = 𝜺𝒊 𝟏 + 𝜺𝒊 𝟐 + ⋯ + 𝜺𝒊 𝑵
The total energy of a collection of N independent molecules is
the sum of the energies of the molecules.
19
 Fluctuations from the most probable distribution
𝑵𝒊 𝒆−𝜷𝑬𝒊
 = −𝜷𝑬𝒊 gives the probability of occurrence of ensemble members in
𝑵 𝒊𝒆
a single state i of the entire system of energy Ei. There may in fact be
numerous states with almost identical energies.

The energy density of states is the number of states

in an energy range divided by the width of the range.

 The most members of the ensemble have an energy very close to the
mean value. 20
 Expression of Macroscopic properties in terms of
Canonical Partition Function

𝑁 𝜕𝑞 The average energy 1 𝜕𝑄

𝑈 𝑇 =𝑈 0 +− 𝑈 𝑇 =𝑈 0 +−
𝑞 𝜕𝛽 of a member is 𝐸 = 𝐸/𝑁. 𝑄 𝜕𝛽 𝑉
𝑉

𝑘
𝑆 = 𝑘 ln 𝑊 𝑊= 𝑊𝑁 𝑆= 𝑘 ln 𝑊 1 𝑁 = ln 𝑊
𝑁

𝑁 𝑑𝑞 1 𝑑𝑄
𝑆 𝑇 =− + 𝑁𝑘 ln 𝑞 𝑆 𝑇 =− + 𝑘 ln 𝑄
𝑇𝑞 𝑑𝛽 𝑇𝑄 𝑑𝛽
 Relation between Canonical Partition Function and
Molecular Partition Function
 Consider distinguishable and independent molecules

 The total energy of a collection of N independent molecules is the sum

of the energies of the molecules.
𝑬𝒊 = 𝜺𝒊 𝟏 + 𝜺𝒊 𝟐 + ⋯ + 𝜺𝒊 𝑵

𝑸= 𝒆−𝜷𝑬𝒊
𝒊

𝑸= 𝒆−𝜷𝜺𝒊 𝟏 +𝜷𝜺𝒊 𝟐 +⋯+𝜷𝜺𝒊 𝑵

𝑸= 𝒆−𝜷𝜺𝒊 𝒆−𝜷𝜺𝒊 … 𝒆−𝜷𝜺𝒊

𝒊 𝒊 𝒊
𝑵

𝑸= 𝒆−𝜷𝜺𝒊
𝒊

𝑸 = 𝒒𝑵
22
 What will be Canonical Partition Function for
indistinguishable molecules?

 If all the molecules are identical and free to move through space, Can we
distinguish them? 𝑸 = 𝒒𝑵 Not valid

 Suppose that molecule 1 is in some state a, molecule 2 is in b, and molecule 3 is in

c, What is the energy of this member in Ensemble?
𝑬 = 𝜺𝒂 𝟏 + 𝜺𝒃 𝟐 + 𝜺𝒄 𝟑

 Suppose that molecule 3 is in some state a, molecule 1 is in b, and molecule 2 is in

c, What is the energy of this member in Ensemble?
𝑬 = 𝜺𝒂 𝟑 + 𝜺𝒃 𝟏 + 𝜺𝒄 𝟐

 Is above two member distinguishable or indistinguishable?

 There are 6 such permutation and in general N!

 If we use 𝑸 = 𝒒𝑵 , we are counting more by N! way, So

𝒒𝑵
𝑸=
𝑵!
23
 Argument for 1/N! is approximation in case of
indistinguishable particles and does not hold for low
temperature.

𝑸 = 𝒒𝑵 Not valid for indistinguishable particles

 𝑪𝒐𝒏𝒔𝒊𝒅𝒆𝒓 𝒏𝒐𝒕 𝒍𝒐𝒘 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 𝒐𝒓 𝒄𝒐𝒏𝒔𝒊𝒅𝒆𝒓 𝒆𝒏𝒐𝒖𝒈𝒉 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒓𝒖𝒆. In such
condition for a N particles system, it can occupy different quantum states.

 Then there are N! microstates, but this correspond to same microstate for
indistinguishable particles.

 Suppose that molecule 1 is in some state a, molecule 2 is in b, and molecule 3 is in

c, What is the energy of this member in Ensemble?
𝑬 = 𝜺𝒂 𝟏 + 𝜺𝒃 𝟐 + 𝜺𝒄 𝟑
 Suppose that molecule 3 is in some state a, molecule 1 is in b, and molecule 2 is in
c, What is the energy of this member in Ensemble?
𝑬 = 𝜺𝒂 𝟑 + 𝜺𝒃 𝟏 + 𝜺𝒄 𝟐

𝒒𝑵
𝑸= valid for indistinguishable particles
𝑵! 24
 How to identify distinguishable or indistinguishable?

 For molecules to be indistinguishable, they must be of the same kind.

 Identical molecules in a lattice can therefore be treated as distinguishable

because their sites are distinguishable.

 Identical molecules in a gas are indistinguishable because they are free to move
to different locations, and there is no way of keeping track of the identity of a
given molecule.

25
 Identify the systems for which it is essential to include a factor of 1/N! on going
from Q to q:
(a) a sample of helium gas
(b) a sample of carbon monoxide gas
(c) a solid sample of carbon monoxide
(d) water vapour.
(e) a sample of carbon dioxide gas
(f) a sample of graphite
(g) a sample of diamond
(h) ice.

26
What is the entropy change for the isothermal
expansion of a perfect gas?
𝑑𝑞𝑟𝑒𝑣
𝑑𝑆 =
𝑇

∆𝑈 = 𝑞 + 𝑤

𝑉𝑓
𝑤=− 𝑝𝑒𝑥 𝑉
𝑉𝑖

𝑉𝑓
∆𝑆 = 𝑛𝑅𝑙𝑛
𝑉𝑖

𝑒 5 2 𝑘𝑇
𝑆 𝑇 = 𝑛𝑅 ln Sackur–Tetrode equation
𝑝Λ3

𝑉 = 𝑛𝑅𝑇/𝑝
27
 Explain the molecular interpretation of Entropy
Change with Volume Change for perfect gas

𝑒 5 2 𝑘𝑇
𝑆 𝑇 = 𝑛𝑅 ln Sackur–Tetrode equation
𝑝Λ3

Why?
𝑛2 ℎ2 3ℎ2
𝐸𝑛 = ∆𝐸1−2 =
8𝑚𝐿2 8𝑚𝐿2

What happens to Entropy?

The energy levels become closer together

(as 1/L2), and as a result more are thermally
accessible at a given temperature. Consequently, the
entropy of the system rises as the container expands.

Classical expression is in fact a consequence of the increase in the number of

accessible translational states when the volume of the container is increased 28
 What is the importance of molecular spectroscopy?

 Useful to determine and identify the structure of a chemical:

Chemists, Metallurgists, Astrophysicists, and Environmental Scientists
etc.

 Analysis of molecular spectra leads to values of bond strengths,

lengths, and angles.

 The chemical composition of interstellar space and of planetary

atmospheres can be inferred from the rotational, vibrational, and
electronic spectra of their constituents.

29
 Molecular spectroscopy
 What can happen when photon incident on a molecule or atom?
𝜆𝜈 = 𝑐
 What is photon?
𝜈 1
 Electromagnetic wave 𝜈= =
𝑐 𝜆

𝐸(𝑥, 𝑡) = 𝐸0 cos 2𝜋𝜈𝑡 − (2 𝜋 𝜆)𝑥 + 𝜙

𝐵(𝑥, 𝑡) = 𝐵0 cos 2𝜋𝜈𝑡 − (2 𝜋 𝜆)𝑥 + 𝜙

 Duality Nature of Light

Wave Particle

Photoelectric effect
Constructive

Destructive

Concepts of Modern Physics A. Beiser 31

 Quantization of Energy Levels

Particle Confined in a Box

𝑛2 ℎ2 Classically
𝐸𝑛 = Allowed
8𝑚𝐿2

𝑛 = 1, 2, 3, …

32
 Quantization of Electronic Energy Levels

Electron Confined in a Atom

𝑍 2 𝜇𝑒 4
𝐸𝑛 = −
32𝜋 2 𝜀02 ħ2 𝑛2
𝑛 = 1, 2, 3, … (𝑃𝑟𝑖𝑛𝑐𝑖𝑝𝑎𝑙 𝑄𝑢𝑎𝑛𝑡𝑢𝑚 𝑁𝑢𝑚𝑏𝑒𝑟
Electronic Energy Levels)

𝑍 − 𝐴𝑡𝑜𝑚𝑖𝑐 𝑁𝑢𝑚𝑏𝑒𝑟

𝜇 − 𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑀𝑎𝑠𝑠
ℎ
ħ= , 𝑤ℎ𝑒𝑟𝑒 ℎ 𝑖𝑠 𝑃𝑙𝑎𝑛𝑐𝑘 ′ 𝑠 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
2𝜋

𝜀0 − 𝐷𝑖𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑃𝑒𝑟𝑚𝑖𝑡𝑡𝑖𝑣𝑖𝑡𝑦

Above solution is valid for only

one electron system.
33
 Quantization of Vibrational Energy Levels

Harmonic Oscillator

1
𝐸𝑣 = 𝑣 + ħ𝜔
2

𝑣 = 0, 1, 2, 3, … (𝑉𝑖𝑏𝑟𝑎𝑡𝑖𝑜𝑛𝑎 𝑄𝑢𝑎𝑛𝑡𝑢𝑚
Number)
1 2
𝑘𝑓
𝜔= − 𝐴𝑛𝑔𝑢𝑙𝑎𝑟 𝑓𝑟𝑒𝑞𝑢𝑒𝑛𝑐𝑦
𝑚

ℎ
ħ= , 𝑤ℎ𝑒𝑟𝑒 ℎ 𝑖𝑠 𝑃𝑙𝑎𝑛𝑐𝑘 ′ 𝑠 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
2𝜋

34
 Quantization of Rotational Energy Levels

Rigid Rotor

ħ2
𝐸𝐽 = 𝐽 𝐽 + 1
2𝐼

𝐽 = 0, 1, 2, 3, … (𝑅𝑜𝑡𝑎𝑡𝑖𝑜𝑛𝑎𝑙 𝑄𝑢𝑎𝑛𝑡𝑢𝑚
Number)

Note that the energy separation between

neighbouring levels increases as J increases.

35
0.01 kJ mol-1 10 kJ mol-1 103 kJ mol-1

36
 What physical phenomena can happen when photon
incident on matter?
Bohr frequency Condition
Decides Photon Absorbed Emission
or Emitted Absorption
𝐸2 𝐸2
𝐸2

ℎ𝜈
ℎ𝜈 𝐸1
𝐸1 𝐸1

∆𝐸 = 𝐸2 − 𝐸1 = ℎ𝜈
• 1 in 107 of the incident photons collide with the
Scattering molecules.

• Stokes Radiation: Low energy due to inelastic

scattering.

• While Anti-Stokes Radiation: High energy due to

inelastic scattering.

• Rayleigh: same energy due to elastic Collision.

37
• Raman spectroscopy.
 Spectrometer

 Sources of radiation: Sources of radiation are either monochromatic (narrow

frequency range) or polychromatic (broad frequency range).

 Dispersing Element: The role is to separate wavelengths spatially normally

through diffraction grating.

 Detector: A detector is a device that converts radiation into an electric current

or voltage for appropriate signal processing and display.
38
 Transitions of the electron in the hydrogen atom

𝑍 2 𝜇𝑒 4
𝐸𝑛 = −
32𝜋 2 𝜀02 ħ2 𝑛2

39
 What is difference between atomic and molecular
spectroscopy
0.01 kJ mol-1 10 kJ mol-1 103 kJ mol-1

The difference from atomic spectroscopy is that the

energy of a molecule can change not only as a result of
electronic transitions but also because it can undergo
changes of rotational and vibrational state. Molecular
spectra are therefore more complex than atomic spectra.

40
 Absorption and EmissionSpectroscopy
 In absorption spectroscopy, the net absorption of incident radiation is monitored
as its frequency or wavelength or (wavenumber) is varied.

 Why net absorption?

 When a sample is irradiated, both absorption and emission at a given frequency

are stimulated, and the detector measures the difference, the net absorption.

 The absorption spectrum of chlorophyll.

 Which EM spectrum? Visible region.

 Note that it absorbs in the red and blue regions,

and that green light is not absorbed.

41
 Beer-Lambert Law
 It is found empirically that the transmitted intensity I varies with the length, L,
of the sample and the molar concentration, [J], of the absorbing species J in
accord with the Beer–Lambert law

𝐼 = 𝐼0 10−𝜀 𝐽 𝐿

 where 𝐼0 is the incident intensity. The quantity ε (epsilon) is called the molar
absorption coefficient.

 The molar absorption coefficient depends on the frequency of the incident

radiation and is greatest where the absorption is most intense. Its dimensions
are 1/(concentration × length), and it is normally convenient to express it in cubic
decimetres per mole per centimetre (dm3 mol−1 cm−1); in SI base units it is
expressed in metres-squared per mole (m2 mol−1).

 What does unit of ε (epsilon) indicate about it physical meaning?

 The latter units imply that ε may be regarded as a (molar) cross-section for
absorption and that, the greater the cross-sectional area of the molecule for
absorption, the greater is its ability to block the passage of the incident
radiation at a given frequency.
42
 The spectral characteristics of a sample are commonly reported as the
transmittance, T, of the sample at a given frequency:

𝐼
𝑇=
𝐼0

 The absorbance, A, of the sample:

𝐼0
𝐴 = log
𝐼

 If the transmittance is 0.1 for a path length of 1 cm (corresponding to a 90 per

cent reduction in intensity), then it would be (0.1)2 = 0.01 for a path of double
the length (corresponding to a 99 per cent reduction in intensity overall).

 The two quantities are related by A = −log T (note the common logarithm) and
the Beer–Lambert law becomes

𝐴=ε𝐽 𝐿

43
 𝐴=ε𝐽 𝐿

The maximum value of the molar absorption coefficient, εmax, is an indication of

the intensity of a transition.

44
 Broadening of Spectral Line
 Doppler Broadening: One important broadening process in gaseous samples is
the Doppler effect, in which radiation is shifted in frequency when the source is
moving towards or away from the observer.

The Gaussian shape of a Doppler-broadened spectral line

reflects the Maxwell distribution of speeds in the sample at
the temperature of the experiment.

 Lifetime broadening: It is found that spectroscopic lines from gas-phase

samples are not infinitely sharp even when Doppler broadening has been largely
eliminated by working at low temperatures. This residual broadening is due to
quantum mechanical effects.
ℎ
∆𝐸∆𝑡 ≥
4𝜋

 Lifetime broadening arises from the finite lifetime of an excited state and a
consequent blurring of energy levels. 45